WO2013068479A1 - Self-emulsifiable polyolefine compositions - Google Patents

Self-emulsifiable polyolefine compositions Download PDF

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Publication number
WO2013068479A1
WO2013068479A1 PCT/EP2012/072162 EP2012072162W WO2013068479A1 WO 2013068479 A1 WO2013068479 A1 WO 2013068479A1 EP 2012072162 W EP2012072162 W EP 2012072162W WO 2013068479 A1 WO2013068479 A1 WO 2013068479A1
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Prior art keywords
weight
amount
composition
self
water
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PCT/EP2012/072162
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French (fr)
Inventor
Rainer Dobrawa
Dieter Boeckh
Rajan K. Panandiker
Julie Menkhaus
Frank Huelskoetter
Original Assignee
Basf Se
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Application filed by Basf Se filed Critical Basf Se
Priority to KR1020147015481A priority Critical patent/KR20140096112A/en
Priority to IN3625CHN2014 priority patent/IN2014CN03625A/en
Priority to MX2014005651A priority patent/MX338994B/en
Priority to CN201280055534.3A priority patent/CN104023705B/en
Priority to EP12781347.5A priority patent/EP2776007A1/en
Priority to RU2014123620A priority patent/RU2610439C2/en
Priority to CA2853248A priority patent/CA2853248A1/en
Priority to BR112014011153A priority patent/BR112014011153A2/en
Priority to JP2014540466A priority patent/JP2015502994A/en
Publication of WO2013068479A1 publication Critical patent/WO2013068479A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8111Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/003Organic compounds containing only carbon and hydrogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017Multi-phase liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3749Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/594Mixtures of polymers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention is directed to self-emulsifiable polyolefine compositions, in particular to self-emulsifiable polyisobutene compositions and the use of said emulsions.
  • Polyolefines and in particular polyisobutene(s) are useful ingredients in a lot of technical applications and contribute to improve the feel properties when applied on surfaces such as hair or textile.
  • the formulation of polyisobutene mostly consists in firstly emulsify the polyisobutene in an oil-in-water emulsion and then incorporate the emulsion in an aqueous formulation such as a hair care or laundry formulation, in order to obtain benefits such as emollience, hydrophobi- zation, lubrication or adhesion.
  • Polyisobutene emulsions are exemplified in
  • PCT/EP201 1/057586 which has not yet been published and which discloses an emulsion comprising (a) polyolefines such as polyisobutene, in an amount of from 2 to 75 weight%, (b) polymers Px which are copolymers of non ionic, anionic or pseudocationic monomers in an amount of from 0.05 to 40 weight % and (c) water in an amount of from 10 to 97.95 weight %.
  • WO 2007/042454 A1 describes the use of terpolymers of (a) maleic anhydride, (b) isobutylene and (c) polyisobutylene for producing aqueous emulsions or dispersions of hydrophobic substances such as silicones.
  • WO 2007/014915 writes on aqueous dispersions comprising (A) a polymer such as polyisobutene and (B) an emulsifier obtained by the polymerization of isobutylene, maleic anhydride and polyethyleneglycol. This dispersion is used for the treatment of leather or as additive in construction chemicals.
  • WO2004/154216 describes a copolymer containing polyisobutene, maleic anhydride and poly- alkylene glycols. These copolymers are used as emulsifiers for the preparation of oil-in-water emulsions and find applications e.g. in washing and cleaning formulations, in the cosmetics or pharmaceutical sector.
  • emulsions have to be prepared at high shear rate stirring, which is a complex process in the production scale and involve a high energy input.
  • emulsions are not thermodynamically stable, and can segregate by creaming / sedimen- tation, aggregation and coalescence (phase separation). Creaming is observed when emulsion droplets have a density lower than that of the continuous phase. Such droplets have the tendency to gather on top of the liquid level to form a layer enriched with emulsion droplets.
  • an emulsion which already contains a large amount of water
  • an aqueous formulation such as a hair care or laundry formulation reduces the flexibility of the formulator as to the choice of ingredients and the total concentration of the final formulation.
  • the problem to be solved is to identify a polyolefin composition that has a water content as low as possible or, even better, is completely free of water and that can be emulsified in aqueous formulations and/or water without the need for a high shear emulsification or any other standard emulsification process.
  • the composition should be able to self-emulsify only by stirring it into water or an aqueous formulation.
  • composition according to claims 1 to 12 This goal is surprisingly reached by the composition according to claims 1 to 12.
  • the use of such a composition according to claim 13 forms an additional aspect of the present invention.
  • the prefix (meth) written before a compound means the re- spective unsubstituted compound and/or the compound substituted by the methyl group.
  • (meth)acrylic acid means acrylic acid and/or methacrylic acid
  • (meth)acrylate means acrylate and/or methacrylate
  • (meth)acrylamide means acrylamide and/or methacrylamide.
  • the present invention is directed to a self-emulsifiable composition containing
  • oil(s) Ox in an amount of from 0 to 40 weight %
  • water is not the continuous phase of the composition
  • weight ratio of polyolefine(s) to P x and S x is in the range of from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1.25.
  • the self-emulsifiable composition can consist of components a) and b), in which case the amounts add up to 100 weight %, - such a composition forms a preferred embodiment of the present invention.
  • the composition can also contain components a) and b) as well as additional components.
  • the inventive composition may also contain other components.
  • the amounts, in which the respective compounds are present in the self- emulsifiable composition there exist preferred ranges.
  • a composition according to the invention wherein the components of the self-emulsifiable composition independently of each other are present in amounts of:
  • oil(s) Ox in an amount of from 0 to 40 weight %
  • water is not the continuous phase of the composition
  • weight ratio of polyolefine(s) to P x and S x is in the range of from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1.25.
  • composition wherein the components of the self-emulsifiable composition independently of each other are present in amounts of:
  • water is not the continuous phase of the composition
  • weight ratio of polyolefine(s) to P x and S x is in the range from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1.25.
  • composition wherein the components of the self-emulsifiable composi- tion independently of each other are present in amounts of:
  • water is not the continuous phase of the composition
  • weight ratio of polyolefine(s) to P x and S x is in the range from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1.25.
  • further preferred emulsions are those, which comprise: a) polyolefine(s) in an amount of from 35 to 55 weight%,
  • water is not the continuous phase of the composition
  • weight ratio of polyolefine(s) to P x and S x is in the range from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1 .25 a) polyolefine(s) in an amount of from 50 to 65 weight %,
  • water is not the continuous phase of the composition
  • weight ratio of polyolefine(s) to P x and S x is in the range from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1 .25 a) polyolefine(s) in an amount of from 5 to 20 weight %,
  • water is not the continuous phase of the composition
  • weight ratio of polyolefine(s) to P x and S x is in the range from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1 .25 or a) polyolefine(s) in an amount of from 40 to 60 weight %,
  • water is not the continuous phase of the composition, wherein the weight ratio of polyolefine(s) to P x and S x is in the range from 4:1 to 1 :3 and the weight ratio of Px to S x is higher than 1.25.
  • compositions In order to test whether or not water is the continuous phase of the composition a conductivity measurement is used showing that the compositions have a low conductivity in the range of the pure polyolefine(s), oil(s) or surfactant(s), and not a high conductivity as water.
  • composition according to the invention is self-emulsifiable, i.e. when mixed in an aqueous formulation, simple stirring is required for the composition to form an emulsion.
  • the self-emulsifiable composition is a water-free composition.
  • Water-free compositions are prepared without added water. Nevertheless, there might be minor amounts of residual water originating from the water content of the raw materials.
  • Self- emulsifiable water-free compositions contain less than 2 weight% of water, preferably less than 1 weight% of water, even more preferably, less than 0.5 weight% of water.
  • the self-emulsifiable composition is a water-reduced composition.
  • Water-reduced compositions are prepared by adding a reduced amount of water, in order to reduce the viscosity of the self-emulsifiable composition, so that the total amount of water in the composition lies in the range of from 2 to 8 weight%, preferably from 2 to 6 weight%, even more preferably from 2 to 5 weight%.
  • polyolefine(s) as used in the present invention is/are a chemical compound(s) consisting of carbon and hydrogen atoms.
  • the polyolefine(s) can be linear, e.g. polyethylene, or can have side chains, e.g. polypropylene having methyl-side chains, which side chains may be that long that comb-like structures are found, or can be co- or ter-polymers, e.g. eth- ene/propene-copolymer or ethane/propene/hexane-terpolymer. It is particularly preferred, when the polyolefine(s) is/are substantially homopolymers, i.e.
  • the degree of co- or ter-monomer is below 10 mass%, preferably below 5 mass% based on the mass of the polymer. It is particularly preferred, if the polymer(s) is/are homopolymers, i.e. they consist of only one kind of monomer.
  • a composition, wherein the polyolefin(s) a) is/are selected from the group consisting of: polyethylene, polypropylene, polybutylene and polyisobutylene is preferred.
  • the composition can comprise one or more polyolefine.
  • An emulsion, which only comprises one polyolefine a) is preferred.
  • a composition, which only comprises polyisobutylene as polyolefine a) is particularly preferred.
  • the polyolefines a) can be prepared by the usual procedures (Ullmann's Encyclope- dia of Industrial Chemistry, Polyolefins, Whiteley, Heggs, Koch, Mawer, Immel, Wiley-VCH Ver- lag GmbH & Co. KGaA, Weinheim 2005).
  • the production of polyisobutylene is described e.g. in WO 02/06359 and WO 96/40808 in even more detail.
  • the polyolefine(s) a) preferably has/have of molar mass (Mn) of at least 250 g/mol, preferably at least 350 g/mol and more preferred at least 500 g/mol.
  • the polyolefin(s) a) have a maximum molar mass Mn of 10.000 g/mol, preferably 5000 g/mol and more preferred of 2500 g/mol.
  • the most preferred range of the molar mass Mn of polyolefins a) is from 550 to 2000 g/mol.
  • composition according to the invention comprises polymeric emulsifi- er(s) Px, wherein ⁇ is/are selected from the group consisting of
  • Pi polyisobutene derivatives, wherein Pi is polyisobutenamine, polyisobutene succinic anhydride, a copolymer of polyisobuten succinic anhydride with polyalkylene glycol, a copolymer of polyisobuten succinic anhydride with an oligoamine or with an oligoamine alkoxylate.
  • Polyisobutylene succinic acid is prepared by en-reaction of succinic anhydride and polyisobutylene, as described in DE-A 19519042, DE-A 4319671 , DE-A 4319672 or H. Mach and P. Rath in "Lubrication Science II (1999), S. 175-185.
  • the preparation of polyisobutene and polyisobutene amine is described in EP244616 and references cited therein.
  • Copolymers of polyisobutene succinic anhydride with polyalkylene glycol are described in WO2007/014915.
  • Copolymers of succinic anhydride with oligoamine or with an oligoamine alkoxylate are described in
  • the polyisobutylene part has a molar mass (M n ) of at least 250 g/mol, preferably at least 350 g/mol and more preferred at least 500 g/mol, and a maximum molar mass M n of 10.000 g/mol, preferably 5000 g/mol and more preferred of 2500 g/mol.
  • M n molar mass of the polyisobutylene part
  • the most preferred range of the molar mass M n of the polyisobutylene part is from 550 to 2000 g/mol.
  • Polymer P1 is preferably selected from the group consisting of polyisobutene derivatives, wherein Pi is polyisobutenamine, polyisobutene succinic anhydride, a copolymer of polyisobuten succinic anhydride and polyethylene glycol.
  • Monomer A2 is a cationic monoethylenically unsaturated monomer which is at least partially soluble in water of the reaction solvent, or in the other monomers if no water or solvent is used.
  • Suitable examples of monomer A are (3-acrylamidopropyl)-trimethylammonium chloride (AP- TAC), (3-methacrylamidopropyl)-trimethylammonium chloride (MAPTAC), dimethylaminopropy- lacrylat methochlorid, dimethylaminopropylmethacrylat methochlorid, diallyl dimethyl ammonium chloride (DADMAC).
  • Monomer A is preferably DADMAC.
  • Monomer B2 is a linear or branched alkyl (meth)acrylate, preferably a C10-C30 al- kyl(meth)acrylate, even more preferably a C12-C20 alkyl(meth)acrylate.
  • Suitable monomers B include linear and branched alkyl esters of (meth)acrylic acid, such as octyl acrylate, dodecyl acrylate, lauryl acrylate, cetyl acrylate, octadecyl acrylate, isodecyl acrylate, 2-ethylhexyl acry- late.
  • Monomer B is preferably lauryl acrylate (LA).
  • Monomer C2 is a C3-C8 monoethylenically unsaturated carboxylic acid. Suitable examples of monomer C include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anyhydride, fumaric acid, itaconic acid and alkyli and metal salts thereof. Monomer C is preferably acrylic acid (AA).
  • the polymer P x is preferably the product of the polymerization of
  • Another preferred embodiment is a polymer P2 which is the product of the polymerization of: A2) from 70 to 90 weight % of monomer A2,
  • polymer P2 is a polymeric cationic emulsifier, wherein P2 is the result of the polymerization of
  • R * H, CH 3 ,
  • R H, methyl
  • R' H, methyl
  • n 1 to 200
  • polyalkylene(s) of formula 3 is preferrably composed of:
  • n 1 to 200
  • n 1 to 200
  • the composition can comprise one or more polymers of one or more of the groups Pi), P2) and P3). If two or more polymers of one group and/or of different groups are present, they can be present in equal amounts or in different amounts.
  • esters of C10- to C26-carboxylic acid with C& - C24-alcohols and
  • Preferred oil(s) O x are mineral oils available under the names mineral oil light, mineral oil heavy, paraffin liquid or Nujol, that are liquid at room temperature.
  • mineral oil available from Sigma-Aldrich Chemie GmbH, Kunststoff, under the order number 69808.
  • Particularly preferred oils are silicone oils. Preferred silicone contents are less that 5 weight %, preferably less than 3 weight%, even more preferably less than 1 weight%.
  • Suitable silicone oils are, for example, linear polydimethylsiloxanes,
  • CTFA dimethicone copolyols
  • the number-average molecular weight of the polylsiloxanes is preferably in a range from about 1000 to 150 000 g/mol.
  • a self-emulsifiable composition wherein the surfactant(s) S x is/are selected from the group consisting of:
  • anionic surfactants d2) anionic surfactants and d3) cationic surfactants is preferred.
  • Surfactants normally consist of a hydrophobic and a hydrophilic part.
  • the hydrophobic part normally has a chain length of 4 to 20 C-atoms, preferably 6 to 19 C-atoms and particularly preferred 8 to 18 C-atoms.
  • the functional unit of the hydrophobic group is generally an OH- group, whereby the alcohol can be linear or branched.
  • the hydrophilic part generally consists substantially of alkoxylated units (e.g.
  • ethylene oxide EO
  • propylene oxide PO
  • butyl- ene oxide BO
  • sulfate sulfonate
  • carbonic acids ammonium und ammonium oxide
  • anionic surfactants are: carboxylates, sulfonates, sulfo fatty acid methylesters, sulfates, phosphates.
  • cationic surfactants are: quartery ammonium compounds.
  • betaine-surfactants are: alkyl betaines.
  • non-ionic compounds are: al- cohol alkoxylates.
  • a Treatcarboxylate is a compound, which comprises at least one carboxylate-group in the molecule.
  • Examples of carboxylates, which can be used according to the present invention, are
  • soaps e.g. stearates, oleates, cocoates of alkali metals or of ammonium,
  • ethercarboxylates e.g. Akypo® RO 20, Akypo® RO 50, Akypo® RO 90.
  • a ..sulfonate is a compound, which comprises at least one sulfonate-group in the molecule.
  • sulfonates which can be used according to the invention, are
  • alkyl benzene sulfonates e.g. Lutensit® A-LBS, Lutensit® A-LBN, Lutensit® A-LBA,
  • alkyl sulfonates e.g. Alscoap OS-14P, BIO-TERGE® AS-40, BIO-TERGE® AS-40 CG, BIO-TERGE® AS-90 Beads, Calimulse® AOS-20, Calimulse® AOS-40, Calsoft® AOS-40, Colonial® AOS-40, Elfan® OS 46, Ifrapon® AOS 38, Ifrapon® AOS 38 P, Jeenate® AOS-40, Nikkol® OS-14, Norfox® ALPHA XL, POLYSTEP® A-18, Rhodacal®
  • aromatic sulfonates e.g. Nekal® BX, Dowfax® 2A1.
  • a ..sulfo fatty acid methylester is a compound, having the following general formula (I):
  • R 13 has 10 to 20 C-atoms; preferably 12 to 18 and particularly preferred 14 to 16 C- atoms.
  • a ..sulfate is a compound, which comprises at least one SCvgroup in the molecule.
  • SCvgroup in the molecule.
  • fatty acid alcohol sulfates such as coco fatty alcohol sulfate (CAS 97375-27-4)— e.g.
  • coco fatty alcohol ethersulfates e.g. Emal® 20C, Latemul® E150, Sulfochem® ES-7 i Texapon® ASV-70 Spec, Agnique SLES-229-F, Octosol 828, POLYSTEP® B-23, Uni- pol® 125-E, 130-E, Unipol® ES-40,
  • alcohol ethersulfates e.g. Avanel® S-150, Avanel® S 150 CG, Avanel® S 150 CG N, Witcolate® D51 -51 , Witcolate® D51 -53.
  • a ..phosphate is a compound, which comprises at least one PC group.
  • examples of phosphates, which can be used according to the present invention, are
  • alkyl ether phosphates e.g. Maphos® 37P, Maphos® 54P, Maphos® 37T, Maphos® 210T and Maphos® 21 OP,
  • the anionic surfactants are preferably added as salts.
  • Acceptable salts are e.g. alkali metal salts, such as sodium-, potassium- and lithium salts, and ammonium salts, such as hydroxyl ethylammonium-, di(hydroxy- ethyl)ammonium- and tri(hydroxyethyl)ammonium salts.
  • One group of the cationic surfactants are the quarternary ammonium compounds.
  • a ..quarternary ammonium compound is a compound, which comprises at least one R 4 N + -group per molecule.
  • Examples of counter ions, which are useful in the quarternary ammonium compounds, are
  • Particularly suitable cationic surfactants are:
  • imidazolinquats especially 1 -alkylimidazoliniumsalts of formula II or III
  • R 9 Ci-C 25 -alkyl or C 2 -C 2 5-alkenyl
  • R 10 Ci-C 4 -alkyl or hydroxy-Ci-C 4 -alkyl
  • R 11 Ci-C 4 -alkyl, hydroxy-Ci-C 4 -alkyl or a rest R 1 -(CO)-X-(CH 2 ) m - (X:-0- or -NH-; m: 2 or
  • a Treatbetain-surfactant is a compound, which comprises under conditions of use - i.e. in the case of textile washing under normal pressure and at temperatures of from room temperature to 95 °C - at least one positive charge and at least one negative charge.
  • An instinctalkylbetain is a betain- surfactant, which comprises at least one alkyl-unit per molecule. Examples of betain- surfactants, which can be used according to the invention, are
  • Non-ionic surfactants are interfacially active substances having a head group, which is an uncharged, polar, hydrophilic group, not carrying an ionic charge at neutral pH, and which head group makes the non-ionic surfactant water soluble. Such a surfactant adsorbs at interfaces and aggregates to micelles above the critical micelle concentration (cmc).
  • the hydrophilic head group it can be distinguished between (oligo)oxyalkylene-groups, especially (oligo)oxyethylene-groups, (polyethyleneglycol-groups), including fatty alcohol polyglycol ether (fatty alcohol alkoxylates), alkylphenol polyglycolether and fatty acid ethoxylates, alkox- ylated triglycerides and mixed ethers (polyethylene glycolether alkoxylated on both sides); and carbohydrate-groups, including e.g. alkyl polyglucosides and fatty acid-A/-methylglucamides.
  • fatty alcohol polyglycol ether fatty alcohol alkoxylates
  • alkylphenol polyglycolether alkylphenol polyglycolether
  • mixed ethers polyethylene glycolether alkoxylated on both sides
  • carbohydrate-groups including e.g. alkyl polyglucosides and fatty acid-A/-methylglucamides.
  • Alcohol alkoxylates are based on a hydrophobic part having a chain length of 4 to 20 C-atoms, preferably 6 to 19 C-atoms and particularly preferred 8 to 18 C-atoms, whereby the alcohol can be linear or branched, and a hydrophilic part, which can be alkoxylated units, e.g. ethylene oxide (EO), propylene oxide (PO) and/or butylene oxide (BuO), having 2 to 30 repeating units. Examples are besides others Lutensol ® XP, Lutensol ® XL, Lutensol ® ON, Lutensol ® AT, Lutensol ® A, Lutensol ® AO, Lutensol ® TO.
  • EO ethylene oxide
  • PO propylene oxide
  • BuO butylene oxide
  • Alcoholphenolalkoxylat.es are compounds according to general formula (V),
  • Non-limiting examples of such compounds are: Norfox® OP-102, Surfonic® OP-120, T-Det® 0-12.
  • Fatty acid ethoxylates are fatty acid esters, which have been treated with different amounts of ethylene oxide (EO).
  • Triglycerides are esters of the glycerols (glycerides), in which all three hydroxy-groups have been esterified using fatty acids. These can be modified by alkylene oxides.
  • Fatty acid alkanol amides are compounds of general formula (VI)
  • R 12 comprises 1 1 to 17 C-atoms and 1 ⁇ m + n ⁇ 5.
  • Alkylpolyglycosides are mixtures of alkylmonoglucosides (alkyl- a-D- and - ⁇ -D-glucopyranoside plus small amounts of -glucofuranoside), alkyldiglucosides (-isomaltosides, -maltosides and others) and alkyloligoglucosides (-maltotriosides, -tetraosides and others).
  • Alkylpolyglycosides are among other routes accessible by acid catalysed reaction (Fischer-reaction) from glucose (or starch) or from n-butylglucosides with fatty alcohols. Alkylpolyglycosides fit general formula (VII)
  • Lutensol ® GD70 One example is Lutensol ® GD70.
  • R 6 is a n-Ci2-alkyl-moiety
  • R 7 an alkyl-moiety having 1 to 8 C-atoms.
  • R 7 preferably is methyl.
  • a self-emulsifiable composition wherein the additive(s) A x is/are selected from the group sisting of: disinfectant, dye, acid, base, complexing agent, biocide, hydrotope, thickener, builder, cobuild- er, enzyme, bleaching agent, bleach activator, bleaching catalyst, corrosion inhibitor, dye protection additive, dye transfer inhibitor, anti-greying agent, soil-release-polymer, fiber protection agent, silicon, bactericide, preserving agent, organic solvent, solubility adjustor, solubility en- hancer, perfume, gel formers, dyes, pigments, photoprotective agents, consistency regulators, antioxidants, bleaches, care agents, tints, tanning agents, humectants, refatting agents, collagen, protein hydrolysates, lipids, emollients, softeners, antifoams, antistats, resins, solvents, solubility promoters, neutralizing agents, stabilizers, sterilizing agents, propellants, drying agents, o
  • Disinfectants can be: oxidation agents, halogens such as chlorine and iodine and substances, which release the same, alcohols such as ethanol, 1 -propanol and 2-propanol, aldehydes, phe- noles, ethylene oxide, chlorohexidine and mecetroniummetilsulfate.
  • oxidation agents such as chlorine and iodine and substances, which release the same
  • alcohols such as ethanol, 1 -propanol and 2-propanol
  • aldehydes such as ethanol, 1 -propanol and 2-propanol
  • aldehydes such as ethanol, 1 -propanol and 2-propanol
  • aldehydes such as ethanol, 1 -propanol and 2-propanol
  • aldehydes such as ethanol, 1 -propanol and 2-propanol
  • aldehydes such as ethanol, 1 -propanol and 2-propan
  • Dyes can be besides others: Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101 , Acid Green 1 , Acid Green 25.
  • Acids are compounds that can advantageously be used to solve or to avoid scaling.
  • Non-limiting examples of acids are formic acid, acetic acid, citric acid, hydrochloric acid, sulfuric acid and sulfonic acid.
  • Bases are compounds, which are useful for adjusting a preferable pH-range for complexing agents. Examples of bases, which can be used according to the present invention, are: NaOH, KOH and amine ethanol.
  • zeolites different types are useful, especially those of type A, X, B, P, MAP and HS in their Na-modification or in modifications in which Na is partially substituted by other cat ions such as Li, K, Ca, Mg or ammonium;
  • crystalline silicates such as disilicates and layer-silicates, e.g. ⁇ - and p-Na2Si20s.
  • the silicates can be used as alkali metal-, earth alkali metal- or ammonium salts, the Na-, Li- and Mg-silicates are preferred;
  • amorphous silicates such as sodium metasilicate and amorphous disilicate
  • carbonates and hydrogencarbonates These can be used as alkali metal-, earth alkali metal- or ammonium salts.
  • Na-, Li- and Mg-carbonates and -hydrogen carbonate, especially sodium carbonate and/or sodium hydrogen carbonate are preferred;
  • polyphosphates such as pentanatriumtriphosphate.
  • Oligomeric and polymeric carbonic acids such as homopolymers of acrylic acid and aspartic acid, oligomaleic acid, copolymers of maleic acid and acrylic acid, methacrylic acid or C2-C22- olefines, e.g. isobutene or long chain a-olefines, vinyl-d-Cs-alkylether, vinylacetate, vinylpropi- onate, (meth)acryl acid ester of d-Cs-alcohols and styrene.
  • the oligomeric and polymeric carbonic acids preferably are used as acids or as sodium salts.
  • Chelating agents are compounds, which can bind cat ions. They can be used to reduce water hardness and to precipitate heavy metals. Examples of complexing agents are: NTA, EDTA, MGDA, DTPA, DTPMP, IDS, HEDP, ⁇ -ADA, GLDA, citric acid, oxodisuccinic acid and bu- tanetetracarbonic acid.
  • the advantage of the use of these compounds lies in the fact that many compounds, which serve as cleaning agents, are more active in soft water. In addition to that scaling can be reduced or even be avoided. By using such compounds there is no need to dry a cleaned surface. This is an advantage in the work flow.
  • Useful anti greying agents are e.g. carboxymethylcellulose and graft polymers of vinyl acetate on polyethylene glycol.
  • Useful bleaching agents are e.g. adducts of hydrogenperoxide at inorganic salts, such as sodium perborate-monohydrate, sodium perborate-tetrahydrate and sodium carbonate-perhydrate, and percarbonic acids, such as phthalimidopercapronic acid.
  • bleach activators compounds such as ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetylethylendiamine (TAED), sodium- p-nonanoyloxybenzenesulfonate and N-methylmorpholiniumacetonitrilemethyl-sulfate are useful.
  • TAED ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetylethylendiamine
  • sodium- p-nonanoyloxybenzenesulfonate sodium- p-nonanoyloxybenzenesulfonate
  • N-methylmorpholiniumacetonitrilemethyl-sulfate N-methylmorpholiniumacetonitrilemethyl-sulfate
  • Useful enzymes are e.g. proteases, lipases, amylases, cellulases, mannanases, oxidases and peroxidases.
  • dye transfer inhibitors are e.g. homo-, co- and graft-polymers of 1 -vinylpyrrolidone, 1 - vinylimidazol or 4-vinylpyridine-N-oxide. Also homo- and copolymers of 4-vinyl pyridin, which have been treated with chloro acetic acid are useful dye transfer inhibitors.
  • Biocides are compounds which kill bacteria. An example of a biocide is glutaric aldehyde. The advantage of the use of biocides is that the spreading of pathogenic germs is counteracted.
  • Hydrotropes are compounds which enhance the solubility of the surfactant / the surfactants in the chemical composition. An example is: cumolsulfonate.
  • Thickeners are compounds, which enhance the viscosity of the chemical composition.
  • Non- limiting examples of thickeners are: polyacrylates and hydrophobically modified polyacrylates.
  • the advantage of the use of thickeners is, that liquids having a higher viscosity have a longer residence time on the surface to be treated in the cases this surface is inclined or even vertical. This leads to an enhanced time of interaction.
  • a self-emulsifiable composition which has a content of organic solvent below 50 mg/kg of emulsion is particularly preferred.
  • a self-emulsifiable composition that forms a transparent, homogeneous oil-phase forms one preferred embodiment of the present invention.
  • the self-emulsifiable compositions can be prepared by simply mixing and stirring the compounds a) to e) with each other until a homogeneous composition is obtained.
  • the step of combining the components can vary: in one preferred embodiment, polymer(s) P x is dissolved in polyisobutene, optionally comprising oil(s) and/or additional components, and then optionally combined with surfactants and additional components.
  • polymer(s) P x is optionally mixed with surfactants and/or additional components, and then combined with polyisobutene phase, comprising polyisobutene and optionally oil(s) and/or additional components.
  • aspects of the invention include the use of the self-emulsifiable composition disclosed herein in laundry detergent compositions (e.g., TIDETM), hard surface cleaners (e.g., MR CLEANTM), automatic dishwashing liquids (e.g., CASCADETM), and dishwashing liquids (e.g., DAWNTM).
  • laundry detergent compositions e.g., TIDETM
  • hard surface cleaners e.g., MR CLEANTM
  • automatic dishwashing liquids e.g., CASCADETM
  • dishwashing liquids e.g., DAWNTM
  • Non- limiting examples of cleaning compositions may include those described in U.S. Pat. Nos.
  • the cleaning compositions disclosed herein are typically formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 12, or between about 7.5 and 10.5.
  • Liquid dishwashing product formulations typically have a pH between about 6.8 and about 9.0.
  • Cleaning products are typically formulated to have a pH of from about 7 to about 12. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • Fabric treatment compositions disclosed herein typically comprise a fabric softening active ("FSA") and a nonionic care agent disclosed herein.
  • FSA fabric softening active
  • Suitable fabric softening actives include, but are not limited to, materials selected from the group consisting of quats, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, clays, polysaccharides, fatty oils, polymer latexes and mixtures thereof.
  • compositions may include additional adjunct ingredients.
  • Adjunct ingredients include, but are not limited to, deposition aids, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments.
  • the adjunct ingredients are in addition to an materials that are specifically recited in an embodiment that is disclosed and/or claimed. Each adjunct ingredient may be not essential to Applicants' compositions.
  • compositions do not contain one or more of the following adjuncts materials: a deposition aids, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and per- fume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments.
  • adjuncts when one or more adjuncts are present, such one or more adjuncts may be present as detailed below The following is a non-limiting list of suitable additional adjuncts.
  • the fabric treatment composition may comprise from about 0.01 % to about 10%, from about 0.05 to about 5%, or from about 0.15 to about 3% of a deposition aid.
  • Suitable deposition aids are disclosed in, for example, USPA Serial Number
  • the deposition aid may be a cationic or amphoteric polymer. In another aspect, the deposition aid may be a cationic polymer. Cationic polymers in general and their method of manufacture are known in the literature. In one aspect, the cationic polymer may have a cationic charge density of from about 0.005 to about 23, from about 0.01 to about 12, or from about 0.1 to about 7 milliequivalents/g, at the pH of intended use of the composition. For amine- containing polymers, wherein the charge density depends on the pH of the composition, charge density is measured at the intended use pH of the product. Such pH will generally range from about 2 to about 1 1 , more generally from about 2.5 to about 9.5. Charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeat- ing unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
  • Non-limiting examples of deposition enhancing agents are cationic or amphoteric, polysaccharides, proteins and synthetic polymers.
  • Cationic polysaccharides include cationic cellulose de- rivatives, cationic guar gum derivatives, chitosan and derivatives and cationic starches.
  • Cationic polysaccharides have a molecular weight from about 50,000 to about 2 million, or even from about 100,000 to about 3,500,000.
  • Suitable cationic polysaccharides include cationic cellulose ethers, particularly cationic hydroxyethylcellulose and cationic hydroxypropylcellulose.
  • cationic hydroxyalkyi cellulose examples include those with the INCI name Polyquaterniuml O such as those sold under the trade names UcareTM Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers; Polyquaternium 67 such as those sold under the trade name Softcat SK TM, all of which are marketed by Amerchol Corporation, Edgewater NJ; and Polyquaternium 4 such as those sold under the trade name CelquatTM H200 and CelquatTM L-200 available from National Starch and Chemical Company, Bridgewater, NJ.
  • polysaccharides in- elude Hydroxyethyl cellulose or hydoxypropylcellulose quaternized with glycidyl C12-C22 alkyl dimethyl ammonium chloride.
  • suitable polysaccharides include the polymers with the INCI names Polyquaternium 24 such as those sold under the trade name Quaternium LM 200 by Amerchol Corporation, Edgewater NJ .
  • Cationic starches described by D. B. Solarek in Modified Starches, Properties and Uses published by CRC Press (1986) and in U.S. Pat. No.
  • Cationic galactomannans include cationic guar gums or cationic locust bean gum.
  • An example of a cationic guar gum is a quaternary ammonium derivative of Hydroxypropyl Guar such as those sold under the trade name Jaguar® C13 and Jaguar® Excel available from Rhodia, Inc of Cranbury NJ and N-Hance by Aqualon, Wilmington, DE.
  • Suitable cationic polymers includes those produced by polymerization of eth- ylenically unsaturated monomers using a suitable initiator or catalyst, such as those disclosed in USPN 6,642,200.
  • Suitable polymers may be selected from the group consisting of cationic or amphoteric polysaccharide, polyethylene imine and its derivatives, and a synthetic polymer made by polymerizing one or more cationic monomers selected from the group consisting of N,N-dialkylaminoalkyl acrylate, ⁇ , ⁇ -dialkylaminoalkyl methacrylate, ⁇ , ⁇ -dialkylaminoalkyl acrylamide, N,N- dialkylaminoalkylmethacrylamide, quaternized N, N dialkylaminoalkyl acrylate quaternized N,N- dialkylaminoalkyl methacrylate, quaternized ⁇ , ⁇ -dialkylaminoalkyl acrylamide, quaternized N,N- dialkylaminoalkylmethacrylamide, Methacryloamidopropyl-pentamethyl-1 ,3-propylene-2-ol- ammonium dichloride, N,N,N,N'
  • the polymer may optionally be branched or cross- linked by using branching and crosslinking monomers.
  • Branching and crosslinking monomers include ethylene glycoldiacrylate divinylbenzene, and butadiene.
  • the treatment composition may comprise an amphoteric deposition aid polymer so long as the polymer possesses a net positive charge.
  • Said polymer may have a cationic charge density of about 0.05 milliequivalents/g. to about 18 milliequivalents/g.
  • the deposition aid may be selected from the group consisting of cationic pol- ysaccharide, polyethylene imine and its derivatives, poly(acrylamide-co- diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate) and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co- dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co- methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-co- diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide- me
  • the deposition aid may comprise polyethyleneimine or a polyethyleneimine derivative.
  • a suitable polyethyleneinine useful herein is that sold under the trade name Lupasol® by BASF, SE, and Ludwigshafen, Germany
  • the deposition aid may comprise a cationic acrylic based polymer. In a further aspect, the deposition aid may comprise a cationic polyacrylamide. In another aspect, the deposition aid may comprise a polymer comprising polyacrylamide and polymethacrylami- dopropyl trimethylammonium cation. In another aspect, the deposition aid may comprise poly (acrylamide- N-dimethyl aminoethyl acrylate) and its quaternized derivatives. In this aspect, the deposition aid may be that sold under the trade name Sedipur®, available from BTC Specialty Chemicals, a BASF Group, Florham Park, N.J.
  • the deposition aid may comprise poly (acrylamide-co-methacrylamidopropyltrimethyl ammonium chloride).
  • the deposition aid may comprise a non-acrylamide based polymer, such as that sold under the trade name Rheovis® CDE, available from Ciba Specialty Chemicals, a BASF, SE group, Florham Park, N.J., or as disclosed in USPA 2006/0252668.
  • the deposition aid may be selected from the group consisting of cationic or amphoteric polysaccharides.
  • the deposition aid may be selected from the group consisting of cationic and amphoteric cellulose ethers, cationic or amphoteric galactomannan, cationic guar gum, cationic or amphoteric starch, and combinations thereof
  • Suitable cationic polymers may include alkylamine-epichlorohydrin polymers which are reaction products of amines and oligoamines with epichlorohydrin, for example, those polymers listed in, for example, USPNs 6,642,200 and 6,551 ,986.
  • alkylamine-epichlorohydrin polymers which are reaction products of amines and oligoamines with epichlorohydrin, for example, those polymers listed in, for example, USPNs 6,642,200 and 6,551 ,986.
  • Examples include dimethyl- amine-epichlorohydrin-ethylenediamine, available under the trade name Cartafix® CB and Cartafix® TSF from Clariant, Basle, Switzerland.
  • PAE polyamidoamine- epichlorohydrin
  • PAE resins of polyalkylenepolyamine with polycarboxylic acid.
  • the most common PAE resins are the condensation products of diethylenetriamine with adipic acid followed by a subsequent reaction with epichlorohydrin. They are available from Hercules Inc. of Wilmington DE under the trade name KymeneTM or from BASF SE (Ludwigshafen, Germany) under the trade name LuresinTM .
  • the cationic polymers may contain charge neutralizing anions such that the overall polymer is neutral under ambient conditions.
  • Non-limiting examples of suitable counter ions include chloride, bromide, sulfate, methylsulfate, sulfonate, methylsulfonate, carbonate, bicarbonate, formate, acetate, citrate, nitrate, and mixtures thereof.
  • the weight-average molecular weight of the polymer may be from about 500 Daltons to about 5,000,000 Daltons, or from about 1 ,000 Daltons to about 2,000,000 Daltons, or from about 2,500 Daltons to about 1 ,500,000 Daltons, as determined by size exclusion chromatography relative to polyethylene oxide standards with Rl detection.
  • the MW of the cationic polymer may be from about 500 Daltons to about 37,500 Daltons.
  • the products of the present invention may comprise from about 0.1 1 % to 80% by weight of a surfactant. In one aspect, such compositions may comprise from about 5% to 50% by weight of surfactant.
  • Surfactants utilized can be of the anionic, nonionic, zwitterionic, am- pholytic or cationic type or can comprise compatible mixtures of these types. Detergent surfactants useful herein are described in U.S. Patents 3,664,961 , 3,919,678, 4,222,905, 4,239,659, 6,136,769, 6,020,303, and 6,060,443.
  • Anionic and nonionic surfactants are typically employed if the fabric care product is a laundry detergent.
  • cationic surfactants are typically employed if the fabric care product is a fabric softener.
  • Useful anionic surfactants can themselves be of several different types.
  • water-soluble salts of the higher fatty acids i.e., "soaps"
  • alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, or even from about 12 to about 18 carbon atoms.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyi group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyi is the alkyi portion of aryl groups.
  • alkyi is the alkyi portion of aryl groups.
  • alkyi alkoxy sulfates especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms).
  • Other useful anionic surfactants herein include the water-soluble salts of esters of o sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1 - sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and ⁇ -alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyi group and from about 8 to 20 carbon atoms in the alkane moiety.
  • the anionic surfactant may comprise a C1 1 -C18 alkyi benzene sulfonate surfactant; a C10-C20 alkyi sulfate surfactant; a C10-C18 alkyi alkoxy sulfate surfactant, having an average degree of alkoxylation of from 1 to 30, wherein the alkoxy comprises a C1 - C4 chain and mixtures thereof; a mid-chain branched alkyi sulfate surfactant; a mid-chain branched alkyi alkoxy sulfate surfactant having an average degree of alkoxylation of from 1 to 30, wherein the alkoxy comprises a C1 -C4 chain and mixtures thereof; a C10-C18 alkyi alkoxy carboxylates comprising an average degree of alkoxylation of from 1 to 5; a C12-C20 methyl ester sulfonate surfactant, a C10-C18 alpha-
  • the fabric care compositions of the present invention may further contain a nonionic surfactant.
  • the compositions of the present invention can contain up to about 30%, alternatively from about 0.01 % to about 20%, more alternatively from about 0.1 % to about 10%, by weight of the composition, of a nonionic surfactant.
  • the nonionic surfactant may comprise an ethoxylated nonionic surfactant. Examples of suitable non-ionic surfactants are provided in U.S. Patents. 4,285,841 , 6,150,322, and
  • Suitable for use herein are the ethoxylated alcohols and ethoxylated alkyi phenols of the formula R(OC2H4)n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 20 carbon atoms and alkyi phenyl radicals in which the alkyi groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
  • Suitable nonionic surfactants are those of the formula R1 (OC2H4)nOH, wherein R1 is a C10 - C16 alkyi group or a C8 -C12 alkyi phenyl group, and n is from 3 to about 80.
  • particularly useful materials are condensation products of C9-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants include polyhydroxy fatty acid amides such as N- methyl N-1 -deoxyglucityl cocoamide and N-methyl N-1 -deoxyglucityl oleamide and alkyi poly- saccharides such as the ones described in US 5,332,528. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647.
  • the fabric care compositions of the present invention may contain up to about 30%, alternatively from about 0.01 % to about 20%, more alternatively from about 0.1 % to about 20%, by weight of the composition, of a cationic surfactant.
  • cationic surfactants include those which can deliver fabric care benefits.
  • useful cationic surfactants include: fatty amines; quaternary ammonium surfactants; and imidazoline quat materials.
  • useful cationic surfactants include those disclosed in U.S. Patent Appli- cation number 2005/0164905 A1 and having the general formula (XIII):
  • R1 and R2 each are individually selected from the groups of: C1-C4 alkyl; C1-C4 hydroxy alkyl; benzyl; ⁇ (CnH2nO)xH, wherein:
  • i. x has a value from about 2 to about 5;
  • ii. n has a value of about 1 -4;
  • R3 and R4 are each:
  • R3 is a C8-C22 alkyl and R4 is selected from the group of: C1 -C10 alkyl; C1 -C10 hydroxy alkyl; benzyl; ⁇ (CnH2nO)xH, wherein:
  • n has a value of 1 -4;
  • Fabric Softening Active Compounds-
  • the fabric softening active may comprise, as the principal active, compounds of the following formula:
  • each R may comprise either hydrogen, a short chain C1 -C6, in one aspect a C1 -C3 alkyl or hydroxyalkyl group, for example methyl, ethyl, propyl, hydroxyethyl, and the like, poly(C2-3 alkoxy), polyethoxy, benzyl, or mixtures thereof; each X may independently be (CH2)n, CH2-CH(CH3)- or CH-(CH3)-CH2-; each Y may comprise -0-(0)C-, -C(0)-0-, -NR- C(O)-, or -C(0)-NR-; each m may be 2 or 3; each n may be from 1 to about 4, in one aspect 2; the sum of carbons in each R1 , plus one when Y is -0-(0)C- or -NR-C(O) -, may be C12-C22
  • the softener-compatible anion may comprise chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate. In another aspect, the softener-compatible anion may comprise chloride or methyl sulfate.
  • the fabric softening active may comprise the general formula (XV): [R3N+CH2CH(YR1 )(CH2YR1 )] X- Formula (XV) wherein each Y, R, R1 , and X- have the same meanings as before.
  • Such compounds include those having the formula (XVI):
  • each R may comprise a methyl or ethyl group.
  • each R1 may comprise C15 to C19 group.
  • the diester when specified, it can include the monoester that is present.
  • DEQA (2) is the "propyl" ester quaternary ammonium fabric softener active comprising the formula 1 ,2-di(acyloxy)-3-trimethylammoniopropane chloride.
  • the fabric softening active may comprise the formula (XVII):
  • the fabric softening active may comprise the formula (XVIII):
  • R2 may comprise a C1 -6 alkylene group, in one aspect an ethylene group
  • G may comprise an oxygen atom or an -NR- group
  • A- is as defined below.
  • the fabric softening active may comprise the formula (XIX):
  • the fabric softening active may comprise condensation reaction products of fatty acids with dialkylenetriamines in, e.g., a molecular ratio of about 2:1 , said reaction products containing compounds of the formula(XX):
  • R1 , R2 are defined as above, and R3 may comprise a C1 -6 alkylene group, or an ethylene group and wherein the reaction products may optionally be quaternized by the additional of an alkylating agent such as dimethyl sulfate.
  • an alkylating agent such as dimethyl sulfate.
  • the fabric softening active may comprise the formula (XXI): [R1— C(O)— NR— R2— N(R)2— R3— NR— C(O)— R1 ]+ A- (XXI) wherein R, R1 , R2 and R3 are defined as above; A- is as defined below;
  • the fabric softening active may comprise reaction products of fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1 , said reaction products containing compounds of the formula (XXII):
  • the fabric softening active may comprise the formula (XXIII):
  • the fabric softening active may comprise the formula (XXIV);
  • X1 may comprise a C2-3 alkyl group, in one aspect, an ethyl group
  • X2 and X3 may independently comprise C1 -6 linear or branched alkyl or alkenyl groups, in one aspect, methyl, ethyl or isopropyl groups;
  • R1 and R2 may independently comprise C8-22 linear or branched alkyl or alkenyl groups; characterized in that;
  • Non-limiting examples of fabric softening actives comprising formula (XIV) are N, N-bis(stearoyl- oxy-ethyl) ⁇ , ⁇ -dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) ⁇ , ⁇ -dimethyl ammonium chloride, N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium methyl- sulfate.
  • a non-limiting example of fabric softening actives comprising formula (XVI) is 1 , 2 di (stearoyl- oxy) 3 trimethyl ammoniumpropane chloride.
  • Non-limiting examples of fabric softening actives comprising formula (XVII) may include dial- kylenedimethylammonium salts such as dicanoladimethylammonium chloride,
  • di(hard)tallowdimethylammonium chloride dicanoladimethylammonium methylsulfate An ex- ample of commercially available dialkylenedimethylammonium salts usable in the present invention is dioleyldimethylammonium chloride available from Witco Corporation under the trade name Adogen® 472 and dihardtallow dimethylammonium chloride available from Akzo Nobel Arquad 2HT75.
  • a non-limiting example of fabric softening actives comprising formula (XVIII) may include 1 - methyl-1 -stearoylamidoethyl-2-stearoylimidazolinium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group, R5 is a methyl group and A- is a methyl sulfate anion, available commercially from the Witco Corporation under the trade name Varisoft®.
  • a non-limiting example of fabric softening actives comprising formula (XIX) is 1 - tallowylamidoethyl-2-tallowylimidazoline wherein R1 may comprise an acyclic aliphatic C15-C17 hydrocarbon group, R2 may comprise an ethylene group, and G may comprise a NH group.
  • a non-limiting example of a fabric softening active comprising formula (XX) is the reaction products of fatty acids with diethylenetriamine in a molecular ratio of about 2:1 , said reaction product mixture comprising N,N"-dialkyldiethylenetriamine having the formula (XXV): R1 -C(0)-NH-CH2CH2-NH-CH2CH2-NH-C(0)-R1
  • R1 is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021 , available from Henkel Corporation, and R2 and R3 are divalent ethylene groups.
  • R1 is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021 , available from Henkel Corporation
  • R2 and R3 are divalent ethylene groups.
  • Compound (XXI) is a difatty amidoamine based softener having the formula (XXVI):
  • Formula (XXVI) wherein R1 is an alkyl group is an alkyl group.
  • R1 is an alkyl group.
  • An example of such compound is that commercially available from the Witco Corporation e.g. under the trade name Varisoft® 222LT.
  • An example of a fabric softening active comprising formula (XXII) is the reaction products of fatty acids with N-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1 , said reaction product mixture comprising the formula (XXVII):
  • R1 -C(0) is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021 , available from Henkel Cor- poration.
  • a non-limiting example of a fabric softening active comprising formula (XXIV) is a dialkyl imidazoline diester compound, where the compound is the reaction product of N-(2-hydroxyethyl)- 1 ,2-ethylenediamine or N-(2-hydroxyisopropyl)-1 ,2-ethylenediamine with glycolic acid, esterified with fatty acid, where the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydro- genated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid or a mixture of the above.
  • the anion A- which comprises any softener compatible anion, provides electrical neutrality.
  • the anion used to provide electrical neutrality in these salts is from a strong acid, especially a halide, such as chloride, bromide, or iodide.
  • a halide such as chloride, bromide, or iodide.
  • other anions can be used, such as methylsulfate, ethylsulfate, acetate, formate, sulfate, carbonate, and the like.
  • the anion A may comprise chloride or methylsulfate.
  • the anion in some aspects, may carry a double charge. In this aspect, A- represents half a group.
  • the fabric care and/or treatment composition may comprise a second softening agent selected from the group consisting of polyglycerol esters (PGEs), oily sugar derivatives, and wax emulsions.
  • PGEs polyglycerol esters
  • oily sugar derivatives include those disclosed in USPA 61/089,080.
  • oily sugar derivatives and wax emulsions include those disclosed in USPA 2008-0234165 A1.
  • the compositions may comprise from about 0.001 % to about 0.01 % of an unsaturated aldehyde. In one aspect, the compositions are essentially free of an unsaturated aldehyde. Without being limited by theory, in this aspect, the compositions are less prone to the yellowing effect often encountered with amino-containing agents.
  • compositions may also contain from about 0.1 % to 80% by weight of a builder.
  • Compositions in liquid form generally contain from about 1 % to 10% by weight of the builder component.
  • Compositions in granular form generally contain from about 1 % to 50% by weight of the builder component.
  • Detergent builders are well known in the art and can contain, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhy- droxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potas- sium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. 4,144,226 and U.S. 4,246,495.
  • Other polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuc- cinate and tartrate disuccinate described in U.S.
  • Suitable builder includes may be citric acid.
  • Suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates, such as sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, or from about 1.0 to about 2.4. Also useful are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in U.S. 4,605,509.
  • Dispersants may contain from about 0.1 %, to about 10%, by weight of dis- persants Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may contain at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • the dispersants may also be alkoxylated derivatives of polyamines, and/or quaternized derivatives thereof such as those described in US 4,597,898, 4,676,921 , 4,891 ,160, 4,659,802 and 4,661 ,288.
  • Enzymes - The compositions may contain one or more detergent enzymes which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include hemi- cellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, lig- ninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.
  • a typical combination may be a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.
  • Enzymes can be used at their art-taught levels, for example at levels recommended by suppliers such as Novozymes and Genencor. Typical levels in the compositions are from about 0.0001 % to about 5%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001 % or lower; or they can be used in heavier- duty laundry detergent formulations at higher levels, e.g., about 0.1 % and higher. In accord- ance with a preference of some consumers for "non-biological" detergents, the compositions may be either or both enzyme-containing and enzyme-free.
  • the compositions may also include from about 0.0001 %, from about 0.01 %, from about 0.05% by weight of the compositions to about 10%, about 2%, or even about 1 % by weight of the compositions of one or more dye transfer inhibiting agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • dye transfer inhibiting agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • compositions may contain less than about 5%, or from about 0.01 % to about 3% of a chelant such as citrates; nitrogen-containing, P-free aminocarboxylates such as EDDS, EDTA and DTPA; aminophosphonates such as diethylenetriamine pentamethylenephosphonic acid and, ethylenediamine tetramethylenephosphonic acid; nitrogen-free phosphonates e.g., HEDP; and nitrogen or oxygen containing, P-free carboxylate-free chelants such as compounds of the general class of certain macrocyclic N-ligands such as those known for use in bleach catalyst systems.
  • a chelant such as citrates
  • nitrogen-containing, P-free aminocarboxylates such as EDDS, EDTA and DTPA
  • aminophosphonates such as diethylenetriamine pentamethylenephosphonic acid and, ethylenediamine tetramethylenephosphonic acid
  • nitrogen-free phosphonates e.g., HEDP
  • Brighteners - The compositions may also comprise a brightener (also referred to as "optical brightener”) and may include any compound that exhibits fluorescence, including compounds that absorb UV light and reemit as "blue” visible light.
  • useful brighteners include: derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, five-membered heterocy- cles such as triazoles, pyrazolines, oxazoles, imidiazoles, etc., or six-membered heterocycles (coumarins, naphthalamide, s-triazine, etc.).
  • Cationic, anionic, nonionic, amphoteric and zwit- terionic brighteners can be used.
  • Suitable brighteners include those commercially marketed under the trade name Tinopal-UNPA-GX® by Ciba Specialty Chemicals Corporation, a BASF, SE group; (High Point, NC).
  • Bleach system - Bleach systems suitable for use herein contain one or more bleaching agents.
  • suitable bleaching agents include catalytic metal complexes; activated peroxygen sources; bleach activators; bleach boosters; photobleaches; bleaching enzymes; free radical initiators; H202; hypohalite bleaches; peroxygen sources, including perborate and/or percarbonate and combinations thereof.
  • Suitable bleach activators include perhydrolyz- able esters and perhydrolyzable imides such as, tetraacetyl ethylene diamine, octanoylcaprolac- tam, benzoyloxybenzenesulphonate, nonanoyloxybenzene-'sulphonate, benzoylvalerolactam, dodecanoyloxybenzenesulphonate.
  • Suitable bleach boosters include those described in US Patent 5,817,614.
  • Other bleaching agents include metal complexes of transitional metals with ligands of defined stability constants. Such catalysts are disclosed in U.S. 4,430,243,
  • Stabilizer - The compositions may contain one or more stabilizers and thickeners. Any suitable level of stabilizer may be of use; exemplary levels include from about 0.01 % to about 20%, from about 0.1 % to about 10%, or from about 0.1 % to about 3% by weight of the composition.
  • suitable for use herein include crystalline, hydroxyl-containing stabilizing agents, trihydroxystearin, hydrogenated oil, or a variation thereof, and combinations thereof.
  • the crystalline, hydroxyl-containing stabilizing agents may be water- insoluble wax-like substances, including fatty acid, fatty ester or fatty soap.
  • the crystalline, hydroxyl-containing stabilizing agents may be derivatives of castor oil, such as hydrogenated castor oil derivatives, for example, castor wax.
  • the hydroxyl containing stabilizers are disclosed in US Patents 6,855,680 and 7,294,61 1 .
  • Other stabilizers include thickening stabilizers such as gums and other similar polysaccharides, for example gellan gum, carrageenan gum, and other known types of thickeners and rheological additives.
  • Exemplary stabilizers in this class include gum-type polymers (e.g.
  • adjuncts are suitable for use in the instant compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like.
  • adjuncts are in addition to the components that are supplied via Applicants' perfumes and/or perfume systems.
  • Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments.
  • suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incor- porated by reference.
  • Silicones - Suitable silicones comprise Si-0 moieties and may be selected from (a) non- functionalized siloxane polymers, (b) functionalized siloxane polymers, and combinations thereof.
  • the molecular weight of the organosilicone is usually indicated by the reference to the viscosity of the material.
  • the organosilicones may comprise a viscosity of from about 10 to about 2,000,000 centistokes at 25oC.
  • suitable organosilicones may have a viscosity of from about 10 to about 800,000 centistokes at 25oC.
  • Suitable organo- silicones may be linear, branched or cross-linked. In one aspect, the organosilicones may be linear.
  • the premixes or formulations are assessed “clear”, when the transmittance of the formulation, measured with a CADAS 200 spectrophotometer (Dr. Lange Company) at 650 nm in a 1 cm cuvette is higher than 90%.
  • the premix or formulations are assessed “homogeneous”, when upon visual inspection no creaming / sedimentation or phase separation can be observed after one day.
  • the premixes or formulations are assessed "phase separated” when the mixture separated into clearly recognizable organic and aqueous phases, or if droplets of organic phase could be observed on top of the aqueous phase.
  • Polyisobutene (6.0 g, 60 parts per weight, molecular weight 1000 g/mol) and polyisobutene succinic anhydride (3.0 g, 30 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The mixture was heated to 80°C to reduce viscosity and thus simplify mixing.
  • Example PM1 The mixture is prepared in the same way as Example PM1 , applying the ratios given in the table below. All examples formed homogeneous, clear and stable solutions.
  • Polyisobutene (6.0 g, 60 parts per weight, molecular weight 1000 g/mol) and polyisobutene succinic anhydride (3.0 g, 30 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The mixture was heated to 80°C to reduce viscosity and thus simplify mixing.
  • Polyisobutene (5.0 g, 50 parts per weight, molecular weight 1000 g/mol) , polyisobuteneamine (3.25 g, 32.5 parts per weight) and n-paraffin C5-C20 (1 .75 g, 17.5 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar.
  • the composition is a homogeneous, clear and stable solution.
  • Polyisobutene (4.0 g, 40 parts per weight, molecular weight 1000 g/mol) , polyisobuteneamine (3.9 g, 39.0 parts per weight) and n-paraffin C5-C20 (2.1 g, 21.0 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar.
  • the composition is a homogeneous, clear and stable solution.
  • Polyisobutene (1 .0 g, 10 parts per weight, molecular weight 1000 g/mol) , polyisobuteneamine (5.85 g, 58.5 parts per weight) and n-paraffin C5-C20 (3.15 g, 31.5 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar.
  • the composition is a homogeneous, clear and stable solution.
  • Polyisobutene (24.0 g, molecular weight 1000 g/mol) and polyisobutene succinic anhydride ( 12.0 g) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The mixture is heated to 80°C to reduce viscosity and thus simplify mixing.
  • a mixture of nonionic surfactant C10-Guerbetalcohol alkoxylate (HLB 12.5) (4.0 g) and water (2.0 g) is added and the mixture is stirred for 30 min, yielding an emulsifiable polyisobutene composition in the form of a homogeneous clear stable solution.
  • the cleaning and/or treatment compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. 5,879,584; U.S. 5,691 ,297; U.S. 5,574,005; U.S. 5,569,645; U.S. 5,565,422; U.S. 5,516,448; U.S. 5,489,392; U.S. 5,486,303 all of which are incorporated herein by reference.
  • Liquid detergent fabric care compositions of Example A were made by mixing together the ingredients listed in the proportions shown;
  • Liquid detergent formulation A (97.80 g) was placed in a 150 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene Premix PM1 (2.20 g) was slowly added to the detergent formulation upon stirring.
  • the resulting turbid polyisobutene containing formula- tion was stirred for another 30 min to form a homogeneous, clear and stable formulation.
  • Liquid detergent formulation A (98.0 g) was placed in a 150 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • the resulting turbid polyisobutene containing formulation was stirred for another 30 min to form a phase-separated turbid mixture with a ring of polyisobutene on top of the liquid level.
  • Cationic polyacrylamide polymer such as a copolymer of acrylamide/[2- (acryloylamino)ethyl]tri-methylammonium chloride (quaternized dimethyl aminoethyl acry- late) available from BASF, AG, Ludwigshafen under the trade name Sedipur ® 544.
  • Fabric softener formulation B (98.0 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene premix PM1 1 (2.0 g) was slowly added to the fabric softener formulation upon stirring.
  • the resulting polyisobutene containing fabric softener formulation was stirred for another 30 min to form a homogeneous stable formulation that did not show any signs of phase separation.
  • Example F16
  • Example F17 The example is prepared analogous to Example F15, with the difference that the Polyisobutene premix PM1 1 is colored with a red, oil-soluble and water-insoluble dye (Sudan Red 7B, Sigma- Aldrich, 20 ppm) and the liquid fabric enhancer is colored with a blue, water-soluble and oil- insoluble dye (Liquitint Blue, Milliken, 20 ppm).
  • the resulting polyisobutene containing formula- tion exhibited a homogeneous, violet color as a result of the perfect emulsification of the water phase and the oil phase, showing not sign of creaming / sedimentation (i.e. no clear blue aqueous phase on top or bottom), as well as not sign of phase separation (i.e. no red oil phase or red oil droplets observable).
  • Example F17 Example F17:
  • Fabric softener formulation B (98.0 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (2.0 g) was slowly added upon stirring. The resulting polyisobutene containing fabric softener formulation was stirred for another 30 min to form a homogeneous stable formulation that did not show any signs of phase separation.
  • Example 7B The example was prepared analogous to Example F17, with the difference that the Polyisobu- tene premix PM5 is colored with a red, oil-soluble and water-insoluble dye (Sudan Red 7B,
  • the liquid fabric enhancer is colored with a blue, water-soluble and oil-insoluble dye (Liquitint Blue, Milliken, 20 ppm).
  • a blue, water-soluble and oil-insoluble dye Liquitint Blue, Milliken, 20 ppm.
  • the resulting polyisobutene containing formulation exhibited a homogeneous, violet color as a result of the perfect emulsification of the water phase and the oil phase, showing not sign of creaming / sedimentation (i.e. no clear blue aque- ous phase on top or bottom), as well as not sign of phase separation (i.e. no red oil phase or red oil droplets observable).
  • Fabric softener formulation B (98.0 g) that is colored with a blue, water-soluble and oil-insoluble dye (Liquitint Blue, Milliken, 20 ppm) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (2.0 g, 1000 g/mol), colored with a red, oil-soluble and water-insoluble dye (Sudan Red 7B, Sigma-Aldrich, 20 ppm) was slowly added to the fabric softener formulation upon stirring.
  • a blue, water-soluble and oil-insoluble dye Liquitint Blue, Milliken, 20 ppm
  • the resulting polyisobutene containing formulation was stirred for another 30 min to form a clearly phase-separated product consisting of a polyisobutene phase forming a red-colored ring at the top of the liquid level and a liquid fabric enhancer phase forming a blue aqueous phase.
  • Liquid Hand Dish Wash formulation compositions prepared by mixing together ingredients shown below.
  • TMBA trimethoxy benzoic acid
  • HEDP is 1 -hydroxyethylidene 1 ,1 -diphosphonic acid
  • the hand dishwash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene premix PM2 (1 .1 g) was slowly added upon stirring.
  • the resulting polyisobutene containing formulation was stirred for another 30 min to form a turbid, homogeneous liquid.
  • the hand dishwash formulation (50g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene premix PM13 (1.54 g) was slowly added upon stirring.
  • the resulting polyisobutene containing formulation was stirred for another 30 min to form a clear homogeneous liquid.
  • the hand dishwash formulation (50g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (molecular weight 1000 g/mol, 1.0 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a turbid liquid with clearly phase separated droplets of polyisobutene on top of the liquid.
  • Cocoamidopropylbetaine (12.5 g, 29.5 % active in water) and sodium laureth sulfate (35.7 g, 29 % active) were mixed with demineralized water (51.8 g) to form a standard shampoo or body- wash formulation.
  • the product can be thickened with 1 .0 g of sodium chloride.
  • the standard shampoo and bodywash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM1 (1 .1 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a turbid, homogeneous liquid.
  • the standard shampoo and bodywash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene premix PM13 (1.54 g) was slowly added upon stirring.
  • the resulting polyisobutene containing formulation was stirred for another 30 min to form a slightly turbid liquid that shows slight creaming upon storage.
  • Dodecylbenzenesulfonate amine salt (20 g, 55% active in water), C10-Guerbetalcohol+7EO (HLB 12.5) (2 g, 100% active) and alkylpolyglucoside (2 g, 70% active) were mixed with water (76 g) to form a standard car shampoo formulation for home users.
  • the standard car wash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene premix PM1 (1 .1 g) was slowly added upon stirring.
  • the resulting polyisobutene containing formulation was stirred for another 30 min to form a slightly turbid, homogeneous liquid.
  • the standard car wash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene premix PM13 (1 .54 g) was slowly added upon stirring.
  • the resulting polyisobutene containing formulation was stirred for another 30 min to form an opaque homogenous liquid.
  • the standard car wash formulation 50 g was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm.
  • Polyisobutene (molecular weight 1000 g/mol, 1 .54 g) was slowly added upon stirring.
  • the resulting polyisobutene containing formulation was stirred for another 30 min to form an inhomogenous, turbid liquid that instantaneously showed creaming and phase separation.
  • PIBSA Polyisobutene Succinic Anhydride
  • all premixes display the same conductivity as the hydrophobic components such as PIB or PIBA, showing that water is not the continuous phase in these premixes.

Abstract

The present invention is directed to self-emulsifiable compositions comprising polyolefines, in particular polyisobutene, the process to obtain said emulsions and the use of said emulsions.

Description

Self-emulsifiable polyolefine compositions
The present invention is directed to self-emulsifiable polyolefine compositions, in particular to self-emulsifiable polyisobutene compositions and the use of said emulsions.
Polyolefines and in particular polyisobutene(s) are useful ingredients in a lot of technical applications and contribute to improve the feel properties when applied on surfaces such as hair or textile. The formulation of polyisobutene mostly consists in firstly emulsify the polyisobutene in an oil-in-water emulsion and then incorporate the emulsion in an aqueous formulation such as a hair care or laundry formulation, in order to obtain benefits such as emollience, hydrophobi- zation, lubrication or adhesion. Polyisobutene emulsions are exemplified in
PCT/EP201 1/057586, which has not yet been published and which discloses an emulsion comprising (a) polyolefines such as polyisobutene, in an amount of from 2 to 75 weight%, (b) polymers Px which are copolymers of non ionic, anionic or pseudocationic monomers in an amount of from 0.05 to 40 weight % and (c) water in an amount of from 10 to 97.95 weight %.
WO 2007/042454 A1 describes the use of terpolymers of (a) maleic anhydride, (b) isobutylene and (c) polyisobutylene for producing aqueous emulsions or dispersions of hydrophobic substances such as silicones.
WO 2007/014915 writes on aqueous dispersions comprising (A) a polymer such as polyisobutene and (B) an emulsifier obtained by the polymerization of isobutylene, maleic anhydride and polyethyleneglycol. This dispersion is used for the treatment of leather or as additive in construction chemicals.
WO2004/154216 describes a copolymer containing polyisobutene, maleic anhydride and poly- alkylene glycols. These copolymers are used as emulsifiers for the preparation of oil-in-water emulsions and find applications e.g. in washing and cleaning formulations, in the cosmetics or pharmaceutical sector.
Nevertheless, the preparation of an emulsion as a formulation ingredient has a number of drawbacks. Firstly, emulsions have to be prepared at high shear rate stirring, which is a complex process in the production scale and involve a high energy input. Secondly, unlike microemul- sions, emulsions are not thermodynamically stable, and can segregate by creaming / sedimen- tation, aggregation and coalescence (phase separation). Creaming is observed when emulsion droplets have a density lower than that of the continuous phase. Such droplets have the tendency to gather on top of the liquid level to form a layer enriched with emulsion droplets. In contrast, droplets having a density higher than that of the continuous phase have the tendency to sink down to the bottom of the liquid, forming a layer enriched with emulsion droplets. This ef- feet is called sedimentation. Whereas creaming and sedimentation are reversible processes, coalescence is an irreversible effect where individual emulsion droplets merge until, in the end, two continuous phases are formed. Creaming, sedimentation and coalescence have to be avoided, at least during the time between production of the emulsion and the introduction of the emulsion in the intended formulation. To guarantee the stability of the emulsion until its application, measures like temperature control - avoiding too high as well as too low temperatures - or the shipment in stirred containers are needed, which adds to complexity in the supply chain as well as to shipping costs.
Besides, the incorporation of an emulsion, which already contains a large amount of water, in an aqueous formulation such as a hair care or laundry formulation reduces the flexibility of the formulator as to the choice of ingredients and the total concentration of the final formulation. The problem to be solved is to identify a polyolefin composition that has a water content as low as possible or, even better, is completely free of water and that can be emulsified in aqueous formulations and/or water without the need for a high shear emulsification or any other standard emulsification process. Ideally, the composition should be able to self-emulsify only by stirring it into water or an aqueous formulation.
This goal is surprisingly reached by the composition according to claims 1 to 12. The use of such a composition according to claim 13 forms an additional aspect of the present invention.
For the purpose of this invention the prefix (meth) written before a compound means the re- spective unsubstituted compound and/or the compound substituted by the methyl group. For instance, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid, (meth)acrylate means acrylate and/or methacrylate, (meth)acrylamide means acrylamide and/or methacrylamide.
Thus the present invention is directed to a self-emulsifiable composition containing
a) polyolefine(s) in an amount of from 5 to 90 weight %,
b) polymeric emulsifier(s) Px in an amount of from 5 to 90 weight %,
c) oil(s) Ox in an amount of from 0 to 40 weight %,
d) surfactant(s) Sx in an amount of from 0 to 40 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range of from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25.
The self-emulsifiable composition can consist of components a) and b), in which case the amounts add up to 100 weight %, - such a composition forms a preferred embodiment of the present invention. The composition can also contain components a) and b) as well as additional components. Compositions, which in addition to components a) and b) also contain components c) and/or d) and/or e) form one preferred embodiment of the invention. The inventive composition may also contain other components. With regard to the amounts, in which the respective compounds are present in the self- emulsifiable composition, there exist preferred ranges. Thus a composition according to the invention, wherein the components of the self-emulsifiable composition independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 20 to 70 weight %,
b) polymer emulsifier(s) Px in an amount of from 10 to 50 weight %,
c) oil(s) Ox in an amount of from 0 to 40 weight %,
d) surfactant(s) Sx in an amount of from 0.1 to 30 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range of from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25.
Even more preferred is a composition, wherein the components of the self-emulsifiable composition independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 30 to 60 weight %,
b) polymer emulsifier(s) Px in an amount of from 20 to 45 weight %,
c) oil(s) Ox in an amount of from 0,1 to 30 weight %,
d) surfactant(s) Sx in an amount of from 0,5 to 25 weight %,
e) additive(s) Ax in an amount of from 0,1 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25.
And most preferred is a composition, wherein the components of the self-emulsifiable composi- tion independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 40 to 50 weight %,
b) polymeric emulsifier(s) Px in an amount of from 25 to 40 weight %,
c) oil(s) Ox in an amount of from 5 to 15 weight %,
d) surfactant(s) Sx in an amount of from 5 to 15 weight %,
e) additive(s) Ax in an amount of from 2 to 8 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25. To maximize the content of polyolefine(s), it is advantageous to reduce the amount of other components in the emulsion. Therefore, further preferred emulsions are those, which comprise: a) polyolefine(s) in an amount of from 35 to 55 weight%,
b) polymeric emulsifier(s) Px in an amount of from 30 to 45 weight %,
c) oil(s) Ox in an amount of 0,1 to 20 weight %,
d) surfactant(s) Sx in an amount of from 5 to 12 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1 .25 a) polyolefine(s) in an amount of from 50 to 65 weight %,
b) polymer(s) Px in an amount of from 25 to 65 weight %,
c) oil(s) Ox in an amount of 0 weight %,
d) surfactant(s) Sx in an amount of from 5 to 12 weight %,
e) additive(s) Ax in an amount of 0 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1 .25 a) polyolefine(s) in an amount of from 5 to 20 weight %,
b) polymer(s) Px in an amount of from 70 to 90 weight %,
c) oil(s) Ox in an amount of 0 to 15 weight %,
d) surfactant(s) Sx in an amount of from 0 weight %,
e) additive(s) Ax in an amount of 0,5 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1 .25 or a) polyolefine(s) in an amount of from 40 to 60 weight %,
b) polymer(s) Px in an amount of from 40 to 60 weight %,
c) oil(s) Ox in an amount of from 0 to 5 weight %,
d) surfactant(s) Sx in an amount of 0 weight %,
e) additive(s) Ax in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition, wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25.
In order to test whether or not water is the continuous phase of the composition a conductivity measurement is used showing that the compositions have a low conductivity in the range of the pure polyolefine(s), oil(s) or surfactant(s), and not a high conductivity as water.
The composition according to the invention is self-emulsifiable, i.e. when mixed in an aqueous formulation, simple stirring is required for the composition to form an emulsion.
In one embodiment of the invention, the self-emulsifiable composition is a water-free composition. Water-free compositions are prepared without added water. Nevertheless, there might be minor amounts of residual water originating from the water content of the raw materials. Self- emulsifiable water-free compositions contain less than 2 weight% of water, preferably less than 1 weight% of water, even more preferably, less than 0.5 weight% of water.
In another embodiment of the invention, the self-emulsifiable composition is a water-reduced composition. Water-reduced compositions are prepared by adding a reduced amount of water, in order to reduce the viscosity of the self-emulsifiable composition, so that the total amount of water in the composition lies in the range of from 2 to 8 weight%, preferably from 2 to 6 weight%, even more preferably from 2 to 5 weight%.
Not only the amount but also the nature of the components of the inventive composition can be chosen advantageously:
In general polyolefine(s) as used in the present invention is/are a chemical compound(s) consisting of carbon and hydrogen atoms. The polyolefine(s) can be linear, e.g. polyethylene, or can have side chains, e.g. polypropylene having methyl-side chains, which side chains may be that long that comb-like structures are found, or can be co- or ter-polymers, e.g. eth- ene/propene-copolymer or ethane/propene/hexane-terpolymer. It is particularly preferred, when the polyolefine(s) is/are substantially homopolymers, i.e. the degree of co- or ter-monomer is below 10 mass%, preferably below 5 mass% based on the mass of the polymer. It is particularly preferred, if the polymer(s) is/are homopolymers, i.e. they consist of only one kind of monomer. In particular a composition, wherein the polyolefin(s) a) is/are selected from the group consisting of: polyethylene, polypropylene, polybutylene and polyisobutylene is preferred. The composition can comprise one or more polyolefine. An emulsion, which only comprises one polyolefine a) is preferred. A composition, which only comprises polyisobutylene as polyolefine a) is particularly preferred. The polyolefines a) can be prepared by the usual procedures (Ullmann's Encyclope- dia of Industrial Chemistry, Polyolefins, Whiteley, Heggs, Koch, Mawer, Immel, Wiley-VCH Ver- lag GmbH & Co. KGaA, Weinheim 2005). The production of polyisobutylene is described e.g. in WO 02/06359 and WO 96/40808 in even more detail. The polyolefine(s) a) preferably has/have of molar mass (Mn) of at least 250 g/mol, preferably at least 350 g/mol and more preferred at least 500 g/mol. The polyolefin(s) a) have a maximum molar mass Mn of 10.000 g/mol, preferably 5000 g/mol and more preferred of 2500 g/mol. The most preferred range of the molar mass Mn of polyolefins a) is from 550 to 2000 g/mol.
Also the self-emulsifiable composition according to the invention comprises polymeric emulsifi- er(s) Px, wherein Ρχ is/are selected from the group consisting of
Pi) polyisobutene derivatives, wherein Pi is polyisobutenamine, polyisobutene succinic anhydride, a copolymer of polyisobuten succinic anhydride with polyalkylene glycol, a copolymer of polyisobuten succinic anhydride with an oligoamine or with an oligoamine alkoxylate.
Polyisobutylene succinic acid is prepared by en-reaction of succinic anhydride and polyisobutylene, as described in DE-A 19519042, DE-A 4319671 , DE-A 4319672 or H. Mach and P. Rath in "Lubrication Science II (1999), S. 175-185. The preparation of polyisobutene and polyisobutene amine is described in EP244616 and references cited therein. Copolymers of polyisobutene succinic anhydride with polyalkylene glycol are described in WO2007/014915. Copolymers of succinic anhydride with oligoamine or with an oligoamine alkoxylate are described in
PCT/EP201 1/057586. For all polyisobutylene derivatives, the polyisobutylene part has a molar mass (Mn) of at least 250 g/mol, preferably at least 350 g/mol and more preferred at least 500 g/mol, and a maximum molar mass Mn of 10.000 g/mol, preferably 5000 g/mol and more preferred of 2500 g/mol. The most preferred range of the molar mass Mn of the polyisobutylene part is from 550 to 2000 g/mol. Polymer P1 is preferably selected from the group consisting of polyisobutene derivatives, wherein Pi is polyisobutenamine, polyisobutene succinic anhydride, a copolymer of polyisobuten succinic anhydride and polyethylene glycol.
P2) polymeric cationic emulsifiers, wherein P2 is the result of the polymerization of
A2) one or more cationic ethylenically unsaturated monomers (monomer A2)
B2) one or more linear or branched alkyl(meth)acrylates (monomer B2),
C2) from 0 to 30 weight % of one or more C3-C8 monoethylenically unsaturated carboxylic acids (monomer C2), Monomer A2 is a cationic monoethylenically unsaturated monomer which is at least partially soluble in water of the reaction solvent, or in the other monomers if no water or solvent is used. Suitable examples of monomer A are (3-acrylamidopropyl)-trimethylammonium chloride (AP- TAC), (3-methacrylamidopropyl)-trimethylammonium chloride (MAPTAC), dimethylaminopropy- lacrylat methochlorid, dimethylaminopropylmethacrylat methochlorid, diallyl dimethyl ammonium chloride (DADMAC). Monomer A is preferably DADMAC. Monomer B2 is a linear or branched alkyl (meth)acrylate, preferably a C10-C30 al- kyl(meth)acrylate, even more preferably a C12-C20 alkyl(meth)acrylate. Suitable monomers B include linear and branched alkyl esters of (meth)acrylic acid, such as octyl acrylate, dodecyl acrylate, lauryl acrylate, cetyl acrylate, octadecyl acrylate, isodecyl acrylate, 2-ethylhexyl acry- late. Monomer B is preferably lauryl acrylate (LA).
Monomer C2 is a C3-C8 monoethylenically unsaturated carboxylic acid. Suitable examples of monomer C include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anyhydride, fumaric acid, itaconic acid and alkyli and metal salts thereof. Monomer C is preferably acrylic acid (AA).
With regard to the amounts in which the respective monomers are present in the polymer P2, there are preferred ranges. Thus the polymer Px is preferably the product of the polymerization of
A2) from 60 to 95 weight % of monomer A2,
B2) from 5 to 45 weight % of monomer B2,
C2) from 0 to 30 weight % of monomer C2.
Even more preferred is a polymer P2 which is the product of the polymerization of:
A2) from 70 to 90 weight % of monomer A2,
B2) from 10 to 35 weight % of monomer B2,
C2) from 5 to 20 weight % of monomer C2.
Another preferred embodiment is a polymer P2 which is the product of the polymerization of: A2) from 70 to 90 weight % of monomer A2,
B2) from 10 to 35 weight % of monomer B2,
C2) 0 weight % of monomer C2.
Most preferably, polymer P2) is a polymeric cationic emulsifier, wherein P2 is the result of the polymerization of
A2) diallyl dimethyl ammonium chloride,
B2) one or more linear or branched alkyl(meth)acrylates,
C2) from 0 to 30 weight % of acrylic acid. P3) being copolymers of polyalkylene(s) of formula 3
Figure imgf000008_0001
3
wherein: R* = H, CH3,
R = H, methyl,
R' = H, methyl,
n = 1 to 200,
with monoethylenically unsaturated monomers.
With regard to copolymers of polyalkylene(s) of formula 3, there exist preferred embodiments. Thus, the polyalkylene(s) of formula 3 is preferrably composed of:
R* = R = R' = Ch
n = 1 to 200
In another embodiment of the invention, polyalkylene(s) of formula 3 is preferably composed of: R* = R = R' = H
n = 1 to 200
The composition can comprise one or more polymers of one or more of the groups Pi), P2) and P3). If two or more polymers of one group and/or of different groups are present, they can be present in equal amounts or in different amounts. A self-emulsifiable composition, wherein the oil(s) Ox is/are selected from the group consisting of:
c1 ) mineral oils, having a boiling point at atmospheric pressure of 150 °C or higher
c2) esters of C10- to C26-carboxylic acid with C& - C24-alcohols and
c3) silicone oils forms a preferred embodiment of the present invention.
Preferred oil(s) Ox are mineral oils available under the names mineral oil light, mineral oil heavy, paraffin liquid or Nujol, that are liquid at room temperature. One example is mineral oil available from Sigma-Aldrich Chemie GmbH, Munich, under the order number 69808. Particularly preferred oils are silicone oils. Preferred silicone contents are less that 5 weight %, preferably less than 3 weight%, even more preferably less than 1 weight%. Suitable silicone oils are, for example, linear polydimethylsiloxanes,
poly(methylphenylsiloxanes), cyclic siloxanes, polyethersiloxanes, dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA)and mix- tures thereof. The number-average molecular weight of the polylsiloxanes is preferably in a range from about 1000 to 150 000 g/mol.
A self-emulsifiable composition, wherein the surfactant(s) Sx is/are selected from the group consisting of:
d1 ) nonionic surfactants,
d2) anionic surfactants and d3) cationic surfactants is preferred.
Surfactants normally consist of a hydrophobic and a hydrophilic part. Thereby the hydrophobic part normally has a chain length of 4 to 20 C-atoms, preferably 6 to 19 C-atoms and particularly preferred 8 to 18 C-atoms. The functional unit of the hydrophobic group is generally an OH- group, whereby the alcohol can be linear or branched. The hydrophilic part generally consists substantially of alkoxylated units (e.g. ethylene oxide (EO), propylene oxide (PO) and/or butyl- ene oxide (BO), whereby generally 2 to 30, preferably 5 to 20 of these alkoxylated units are annealed, and/or charged units such as sulfate, sulfonate, phosphate, carbonic acids, ammonium und ammonium oxide.
Examples of anionic surfactants are: carboxylates, sulfonates, sulfo fatty acid methylesters, sulfates, phosphates. Examples for cationic surfactants are: quartery ammonium compounds. Examples for betaine-surfactants are: alkyl betaines. Examples for non-ionic compounds are: al- cohol alkoxylates.
A„carboxylate" is a compound, which comprises at least one carboxylate-group in the molecule Examples of carboxylates, which can be used according to the present invention, are
> soaps— e.g. stearates, oleates, cocoates of alkali metals or of ammonium,
> ethercarboxylates— e.g. Akypo® RO 20, Akypo® RO 50, Akypo® RO 90.
A ..sulfonate" is a compound, which comprises at least one sulfonate-group in the molecule. Examples of sulfonates, which can be used according to the invention, are
> alkyl benzene sulfonates— e.g. Lutensit® A-LBS, Lutensit® A-LBN, Lutensit® A-LBA,
Marlon® AS3, Maranil® DBS,
> alkyl sulfonates— e.g. Alscoap OS-14P, BIO-TERGE® AS-40, BIO-TERGE® AS-40 CG, BIO-TERGE® AS-90 Beads, Calimulse® AOS-20, Calimulse® AOS-40, Calsoft® AOS-40, Colonial® AOS-40, Elfan® OS 46, Ifrapon® AOS 38, Ifrapon® AOS 38 P, Jeenate® AOS-40, Nikkol® OS-14, Norfox® ALPHA XL, POLYSTEP® A-18, Rhodacal®
A-246L, Rhodacal® LSS-40/A,
> sulfonated oils such as Turkish red oil,
> olefine sulfonates,
> aromatic sulfonates— e.g. Nekal® BX, Dowfax® 2A1.
A ..sulfo fatty acid methylester" is a compound, having the following general formula (I):
Figure imgf000010_0001
wherein R13 has 10 to 20 C-atoms; preferably 12 to 18 and particularly preferred 14 to 16 C- atoms.
A ..sulfate" is a compound, which comprises at least one SCvgroup in the molecule. Examples of sulfates, which can be used according to the present invention, are
> fatty acid alcohol sulfates such as coco fatty alcohol sulfate (CAS 97375-27-4)— e.g.
EMAL® 10G, Dispersogen® SI, Elfan® 280, Mackol® 100N,
> other alcohol sulfates— e.g. Emal® 71 , Lanette® E,
> coco fatty alcohol ethersulfates— e.g. Emal® 20C, Latemul® E150, Sulfochem® ES-7i Texapon® ASV-70 Spec, Agnique SLES-229-F, Octosol 828, POLYSTEP® B-23, Uni- pol® 125-E, 130-E, Unipol® ES-40,
> other alcohol ethersulfates— e.g. Avanel® S-150, Avanel® S 150 CG, Avanel® S 150 CG N, Witcolate® D51 -51 , Witcolate® D51 -53.
A ..phosphate" is a compound, which comprises at least one PC group. Examples of phosphates, which can be used according to the present invention, are
> alkyl ether phosphates— e.g. Maphos® 37P, Maphos® 54P, Maphos® 37T, Maphos® 210T and Maphos® 21 OP,
> phosphates such as Lutensit A-EP,
> alkyl phosphates.
When producing the chemical composition of the present invention the anionic surfactants are preferably added as salts. Acceptable salts are e.g. alkali metal salts, such as sodium-, potassium- and lithium salts, and ammonium salts, such as hydroxyl ethylammonium-, di(hydroxy- ethyl)ammonium- and tri(hydroxyethyl)ammonium salts.
One group of the cationic surfactants are the quarternary ammonium compounds.
A ..quarternary ammonium compound" is a compound, which comprises at least one R4N+-group per molecule. Examples of counter ions, which are useful in the quarternary ammonium compounds, are
> halogens, methosulfates, sulfates and carbonates of coco fat-, sebaceous fat- or ce- tyl/oleyltrimethylammonium.
Particularly suitable cationic surfactants are:
N,N-dimethyl-N-(hydroxy-C7-C25-alkyl)ammonium salts;
mono- and di-(C7-C25-alkyl)dimethylammonium compounds, which were quarternised with alkylating agents esterquats, especially mono-, di- and trialkanolamines, quarternary esterified by Cs-C22- carbonic acids;
imidazolinquats, especially 1 -alkylimidazoliniumsalts of formula II or III
Figure imgf000012_0001
wherein the variables have the following meaning:
R9 Ci-C25-alkyl or C2-C25-alkenyl;
R10 Ci-C4-alkyl or hydroxy-Ci-C4-alkyl;
R11 Ci-C4-alkyl, hydroxy-Ci-C4-alkyl or a rest R1-(CO)-X-(CH2)m- (X:-0- or -NH-; m: 2 or
3),
whereby at least one rest R9 is C7-C22-alkyl.
A„betain-surfactant" is a compound, which comprises under conditions of use - i.e. in the case of textile washing under normal pressure and at temperatures of from room temperature to 95 °C - at least one positive charge and at least one negative charge. An„alkylbetain" is a betain- surfactant, which comprises at least one alkyl-unit per molecule. Examples of betain- surfactants, which can be used according to the invention, are
Cocamidopropylbetain— e.g. MAFO® CAB, Amonyl® 380 BA, AMPHOSOL® CA, AMPHO- SOL® CG, AMPHOSOL® CR, AMPHOSOL® HCG; AMPHOSOL® HCG-50, Chembetaine® C, Chembetaine® CGF, Chembetaine® CL, Dehyton® PK, Dehyton® PK 45, Emery® 6744, Em- pigen® BS/F, Empigen® BS/FA, Empigen® BS/P, Genagen® CAB, Lonzaine® C, Lonzaine® CO, Mirataine® BET-C-30, Mirataine® CB, Monateric® CAB, Naxaine® C, Naxaine® CO, Norfox® CAPB, Norfox® Coco Betaine, Ralufon® 414, TEGO®-Betain CKD, TEGO® Betain E KE 1 , TEGO®-Betain F, TEGO®-Betain F 50 and aminoxides such as alkyl dimethyl amineoxi- de, i.e. compounds of general formula (IV)
R1
1 1
R— N→O (IV)
' 1
R
whereby R1 are different or identical and independently from each other selected from an aliphatic, cyclic or tertiary alkyl- or amido alkyl-moiety, e.g. Mazox® LDA, Genaminox®, Aromox® 14 DW 970. Non-ionic surfactants are interfacially active substances having a head group, which is an uncharged, polar, hydrophilic group, not carrying an ionic charge at neutral pH, and which head group makes the non-ionic surfactant water soluble. Such a surfactant adsorbs at interfaces and aggregates to micelles above the critical micelle concentration (cmc). According to the type of the hydrophilic head group it can be distinguished between (oligo)oxyalkylene-groups, especially (oligo)oxyethylene-groups, (polyethyleneglycol-groups), including fatty alcohol polyglycol ether (fatty alcohol alkoxylates), alkylphenol polyglycolether and fatty acid ethoxylates, alkox- ylated triglycerides and mixed ethers (polyethylene glycolether alkoxylated on both sides); and carbohydrate-groups, including e.g. alkyl polyglucosides and fatty acid-A/-methylglucamides.
Alcohol alkoxylates, are based on a hydrophobic part having a chain length of 4 to 20 C-atoms, preferably 6 to 19 C-atoms and particularly preferred 8 to 18 C-atoms, whereby the alcohol can be linear or branched, and a hydrophilic part, which can be alkoxylated units, e.g. ethylene oxide (EO), propylene oxide (PO) and/or butylene oxide (BuO), having 2 to 30 repeating units. Examples are besides others Lutensol ® XP, Lutensol ® XL, Lutensol ® ON, Lutensol ® AT, Lutensol ® A, Lutensol ® AO, Lutensol ® TO.
Alcoholphenolalkoxylat.es are compounds according to general formula (V),
Figure imgf000013_0001
which can be produced by addition of alkylene oxide, preferably ethylene oxide onto alkyl phenols. R4 is selected from C-iCio-alkyl and hydrogen, preferably R4 = H. It is also preferred, if R5 = H; in the same way it is preferred if R5 = CH3, or, if R5 = CH2CH3. A compound is especially preferred, in which octyl- [(R3 are identical and each hydrogen, R2 = 1 ,1 ,3,3-tetramethylbutyl (diisobutylene)], nonyl- [(R3 are identical and each hydrogen, R2 = 1 ,3,5-trimethylhexyl (tripro- pylene)], dodecyl-, dinonyl- or tributylphenolpolyglycolether (e.g. EO, PO, BuO), R-C6H4-O- (EO/PO/BuO)n with R4 = Cs to C12 alkyl and x = 5 to 10, are present. Non-limiting examples of such compounds are: Norfox® OP-102, Surfonic® OP-120, T-Det® 0-12.
Fatty acid ethoxylates are fatty acid esters, which have been treated with different amounts of ethylene oxide (EO).
Triglycerides are esters of the glycerols (glycerides), in which all three hydroxy-groups have been esterified using fatty acids. These can be modified by alkylene oxides.
Fatty acid alkanol amides are compounds of general formula (VI)
Figure imgf000014_0001
which comprise at least one amide-group having one alkyl moiety R12 and one or two alkoxyl- moiety(ies), whereby R12 comprises 1 1 to 17 C-atoms and 1 < m + n < 5.
Alkylpolyglycosides are mixtures of alkylmonoglucosides (alkyl- a-D- and - β-D-glucopyranoside plus small amounts of -glucofuranoside), alkyldiglucosides (-isomaltosides, -maltosides and others) and alkyloligoglucosides (-maltotriosides, -tetraosides and others). Alkylpolyglycosides are among other routes accessible by acid catalysed reaction (Fischer-reaction) from glucose (or starch) or from n-butylglucosides with fatty alcohols. Alkylpolyglycosides fit general formula (VII)
Figure imgf000014_0002
with
r = 0 to 3 and
s = 4 to 20.
One example is Lutensol ® GD70.
In the group of non-ionic /V-alkylated, preferably /V-methylated, fatty acid amides of general formula (VIII)
Figure imgf000014_0003
R6 is a n-Ci2-alkyl-moiety, R7 an alkyl-moiety having 1 to 8 C-atoms. R7 preferably is methyl.
A self-emulsifiable composition, wherein the additive(s) Ax is/are selected from the group sisting of: disinfectant, dye, acid, base, complexing agent, biocide, hydrotope, thickener, builder, cobuild- er, enzyme, bleaching agent, bleach activator, bleaching catalyst, corrosion inhibitor, dye protection additive, dye transfer inhibitor, anti-greying agent, soil-release-polymer, fiber protection agent, silicon, bactericide, preserving agent, organic solvent, solubility adjustor, solubility en- hancer, perfume, gel formers, dyes, pigments, photoprotective agents, consistency regulators, antioxidants, bleaches, care agents, tints, tanning agents, humectants, refatting agents, collagen, protein hydrolysates, lipids, emollients, softeners, antifoams, antistats, resins, solvents, solubility promoters, neutralizing agents, stabilizers, sterilizing agents, propellants, drying agents, opacifiers is preferred.
Disinfectants can be: oxidation agents, halogens such as chlorine and iodine and substances, which release the same, alcohols such as ethanol, 1 -propanol and 2-propanol, aldehydes, phe- noles, ethylene oxide, chlorohexidine and mecetroniummetilsulfate. The advantage of using disinfectants is that pathogenic germs can hardly grow. Pathogenic germs can be: bacteria, spores, fungi and viruses.
Dyes can be besides others: Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101 , Acid Green 1 , Acid Green 25.
Acids are compounds that can advantageously be used to solve or to avoid scaling. Non-limiting examples of acids are formic acid, acetic acid, citric acid, hydrochloric acid, sulfuric acid and sulfonic acid. Bases are compounds, which are useful for adjusting a preferable pH-range for complexing agents. Examples of bases, which can be used according to the present invention, are: NaOH, KOH and amine ethanol.
As inorganic builder the following are especially useful:
- crystalline and amorphous alumino silicates having ion exchanging properties, such as zeolites: different types of zeolites are useful, especially those of type A, X, B, P, MAP and HS in their Na-modification or in modifications in which Na is partially substituted by other cat ions such as Li, K, Ca, Mg or ammonium;
crystalline silicates, such as disilicates and layer-silicates, e.g. δ- and p-Na2Si20s. The silicates can be used as alkali metal-, earth alkali metal- or ammonium salts, the Na-, Li- and Mg-silicates are preferred;
amorphous silicates, such as sodium metasilicate and amorphous disilicate; carbonates and hydrogencarbonates: These can be used as alkali metal-, earth alkali metal- or ammonium salts. Na-, Li- and Mg-carbonates and -hydrogen carbonate, especially sodium carbonate and/or sodium hydrogen carbonate are preferred;
polyphosphates, such as pentanatriumtriphosphate.
Useful as oligomeric and polymeric cobuilders are:
Oligomeric and polymeric carbonic acids, such as homopolymers of acrylic acid and aspartic acid, oligomaleic acid, copolymers of maleic acid and acrylic acid, methacrylic acid or C2-C22- olefines, e.g. isobutene or long chain a-olefines, vinyl-d-Cs-alkylether, vinylacetate, vinylpropi- onate, (meth)acryl acid ester of d-Cs-alcohols and styrene. Preferred are the homopolymers of acrylic acid and the copolymers of acrylic acid with maleic acid. The oligomeric and polymeric carbonic acids preferably are used as acids or as sodium salts.
Chelating agents are compounds, which can bind cat ions. They can be used to reduce water hardness and to precipitate heavy metals. Examples of complexing agents are: NTA, EDTA, MGDA, DTPA, DTPMP, IDS, HEDP, β-ADA, GLDA, citric acid, oxodisuccinic acid and bu- tanetetracarbonic acid. The advantage of the use of these compounds lies in the fact that many compounds, which serve as cleaning agents, are more active in soft water. In addition to that scaling can be reduced or even be avoided. By using such compounds there is no need to dry a cleaned surface. This is an advantage in the work flow.
Useful anti greying agents are e.g. carboxymethylcellulose and graft polymers of vinyl acetate on polyethylene glycol. Useful bleaching agents are e.g. adducts of hydrogenperoxide at inorganic salts, such as sodium perborate-monohydrate, sodium perborate-tetrahydrate and sodium carbonate-perhydrate, and percarbonic acids, such as phthalimidopercapronic acid.
As bleach activators compounds such as Ν,Ν,Ν',Ν'-tetraacetylethylendiamine (TAED), sodium- p-nonanoyloxybenzenesulfonate and N-methylmorpholiniumacetonitrilemethyl-sulfate are useful.
Useful enzymes are e.g. proteases, lipases, amylases, cellulases, mannanases, oxidases and peroxidases.
Useful as dye transfer inhibitors are e.g. homo-, co- and graft-polymers of 1 -vinylpyrrolidone, 1 - vinylimidazol or 4-vinylpyridine-N-oxide. Also homo- and copolymers of 4-vinyl pyridin, which have been treated with chloro acetic acid are useful dye transfer inhibitors. Biocides are compounds which kill bacteria. An example of a biocide is glutaric aldehyde. The advantage of the use of biocides is that the spreading of pathogenic germs is counteracted. Hydrotropes are compounds which enhance the solubility of the surfactant / the surfactants in the chemical composition. An example is: cumolsulfonate.
Thickeners are compounds, which enhance the viscosity of the chemical composition. Non- limiting examples of thickeners are: polyacrylates and hydrophobically modified polyacrylates. The advantage of the use of thickeners is, that liquids having a higher viscosity have a longer residence time on the surface to be treated in the cases this surface is inclined or even vertical. This leads to an enhanced time of interaction. A self-emulsifiable composition, which has a content of organic solvent below 50 mg/kg of emulsion is particularly preferred.
A self-emulsifiable composition that forms a transparent, homogeneous oil-phase forms one preferred embodiment of the present invention.
The self-emulsifiable compositions can be prepared by simply mixing and stirring the compounds a) to e) with each other until a homogeneous composition is obtained.
The step of combining the components can vary: in one preferred embodiment, polymer(s) Px is dissolved in polyisobutene, optionally comprising oil(s) and/or additional components, and then optionally combined with surfactants and additional components.
In another preferred embodiment, polymer(s) Px is optionally mixed with surfactants and/or additional components, and then combined with polyisobutene phase, comprising polyisobutene and optionally oil(s) and/or additional components.
The use of the self-emulsifiable composition as described above in chemical technical applications, car wash, cosmetics, plant protection, preparation and treatment of paper, textiles and leather, adhesives, dye and pigment formulations, coatings, pharmaceutical applications, con- struction, wood treatment forms another aspect of the present invention.
The use of the self-emulsifiable composition as described above in car wash, forms another aspect of the present invention. Aspects of the invention include the use of the self-emulsifiable composition disclosed herein in laundry detergent compositions (e.g., TIDE™), hard surface cleaners (e.g., MR CLEAN™), automatic dishwashing liquids (e.g., CASCADE™), and dishwashing liquids (e.g., DAWN™). Non- limiting examples of cleaning compositions may include those described in U.S. Pat. Nos.
4,515,705; 4,537,706; 4,537,707; 4,550,862; 4,561 ,998; 4,597,898; 4,968,451 ; 5,565,145;
5,929,022; 6,294,514; and 6,376,445. The cleaning compositions disclosed herein are typically formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 12, or between about 7.5 and 10.5. Liquid dishwashing product formulations typically have a pH between about 6.8 and about 9.0. Cleaning products are typically formulated to have a pH of from about 7 to about 12. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
Fabric treatment compositions disclosed herein typically comprise a fabric softening active ("FSA") and a nonionic care agent disclosed herein. Suitable fabric softening actives, include, but are not limited to, materials selected from the group consisting of quats, amines, fatty esters, sucrose esters, silicones, dispersible polyolefins, clays, polysaccharides, fatty oils, polymer latexes and mixtures thereof.
Additional Fabric and/or Home care Ingredients
The disclosed compositions may include additional adjunct ingredients. Adjunct ingredients include, but are not limited to, deposition aids, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. The adjunct ingredients are in addition to an materials that are specifically recited in an embodiment that is disclosed and/or claimed. Each adjunct ingredient may be not essential to Applicants' compositions. Thus, certain embodiments of Applicants' compositions do not contain one or more of the following adjuncts materials: a deposition aids, bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and per- fume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below The following is a non-limiting list of suitable additional adjuncts.
Deposition Aid - In one aspect, the fabric treatment composition may comprise from about 0.01 % to about 10%, from about 0.05 to about 5%, or from about 0.15 to about 3% of a deposition aid. Suitable deposition aids are disclosed in, for example, USPA Serial Number
12/080,358.
In one aspect, the deposition aid may be a cationic or amphoteric polymer. In another aspect, the deposition aid may be a cationic polymer. Cationic polymers in general and their method of manufacture are known in the literature. In one aspect, the cationic polymer may have a cationic charge density of from about 0.005 to about 23, from about 0.01 to about 12, or from about 0.1 to about 7 milliequivalents/g, at the pH of intended use of the composition. For amine- containing polymers, wherein the charge density depends on the pH of the composition, charge density is measured at the intended use pH of the product. Such pH will generally range from about 2 to about 1 1 , more generally from about 2.5 to about 9.5. Charge density is calculated by dividing the number of net charges per repeating unit by the molecular weight of the repeat- ing unit. The positive charges may be located on the backbone of the polymers and/or the side chains of polymers.
Non-limiting examples of deposition enhancing agents are cationic or amphoteric, polysaccharides, proteins and synthetic polymers. Cationic polysaccharides include cationic cellulose de- rivatives, cationic guar gum derivatives, chitosan and derivatives and cationic starches. Cationic polysaccharides have a molecular weight from about 50,000 to about 2 million, or even from about 100,000 to about 3,500,000. Suitable cationic polysaccharides include cationic cellulose ethers, particularly cationic hydroxyethylcellulose and cationic hydroxypropylcellulose. Examples of cationic hydroxyalkyi cellulose include those with the INCI name Polyquaterniuml O such as those sold under the trade names UcareTM Polymer JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers; Polyquaternium 67 such as those sold under the trade name Softcat SK TM, all of which are marketed by Amerchol Corporation, Edgewater NJ; and Polyquaternium 4 such as those sold under the trade name CelquatTM H200 and CelquatTM L-200 available from National Starch and Chemical Company, Bridgewater, NJ. Other suitable polysaccharides in- elude Hydroxyethyl cellulose or hydoxypropylcellulose quaternized with glycidyl C12-C22 alkyl dimethyl ammonium chloride. Examples of such polysaccharides include the polymers with the INCI names Polyquaternium 24 such as those sold under the trade name Quaternium LM 200 by Amerchol Corporation, Edgewater NJ . Cationic starches described by D. B. Solarek in Modified Starches, Properties and Uses published by CRC Press (1986) and in U.S. Pat. No.
7,135,451 , col. 2, line 33 - col. 4, line 67. Cationic galactomannans include cationic guar gums or cationic locust bean gum. An example of a cationic guar gum is a quaternary ammonium derivative of Hydroxypropyl Guar such as those sold under the trade name Jaguar® C13 and Jaguar® Excel available from Rhodia, Inc of Cranbury NJ and N-Hance by Aqualon, Wilmington, DE.
Another group of suitable cationic polymers includes those produced by polymerization of eth- ylenically unsaturated monomers using a suitable initiator or catalyst, such as those disclosed in USPN 6,642,200.
Suitable polymers may be selected from the group consisting of cationic or amphoteric polysaccharide, polyethylene imine and its derivatives, and a synthetic polymer made by polymerizing one or more cationic monomers selected from the group consisting of N,N-dialkylaminoalkyl acrylate, Ν,Ν-dialkylaminoalkyl methacrylate, Ν,Ν-dialkylaminoalkyl acrylamide, N,N- dialkylaminoalkylmethacrylamide, quaternized N, N dialkylaminoalkyl acrylate quaternized N,N- dialkylaminoalkyl methacrylate, quaternized Ν,Ν-dialkylaminoalkyl acrylamide, quaternized N,N- dialkylaminoalkylmethacrylamide, Methacryloamidopropyl-pentamethyl-1 ,3-propylene-2-ol- ammonium dichloride, N,N,N,N',N',N",N"-heptamethyl-N"-3-(1 -oxo-2-methyl-2- pro- penyl)aminopropyl-9- oxo-8-azo-decane-1 ,4,10-triammonium trichloride, vinylamine and its derivatives, allylamine and its derivatives, vinyl imidazole, quaternized vinyl imidazole and diallyl dialkyl ammonium chloride and combinations thereof, and optionally a second monomer selected from the group consisting of acrylamide, Ν,Ν-dialkyl acrylamide, methacrylamide, N,N- dialkylmethacrylamide, C1 -C12 alkyl acrylate, C1 -C12 hydroxyalkyi acrylate, polyalkylene glyol acrylate, C1 -C12 alkyl methacrylate, C1 -C12 hydroxyalkyi methacrylate, polyalkylene glycol methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and derivatives, acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylme- thane sulfonic acid (AMPS) and their salts. The polymer may optionally be branched or cross- linked by using branching and crosslinking monomers. Branching and crosslinking monomers include ethylene glycoldiacrylate divinylbenzene, and butadiene. In another aspect, the treatment composition may comprise an amphoteric deposition aid polymer so long as the polymer possesses a net positive charge. Said polymer may have a cationic charge density of about 0.05 milliequivalents/g. to about 18 milliequivalents/g.
In another aspect, the deposition aid may be selected from the group consisting of cationic pol- ysaccharide, polyethylene imine and its derivatives, poly(acrylamide-co- diallyldimethylammonium chloride), poly(acrylamide-methacrylamidopropyltrimethyl ammonium chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its quaternized derivatives, poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate) and its quaternized derivative, poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co- dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co- methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-co- diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide- methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid), poly(diallyldimethyl ammonium chloride), poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate), poly(ethyl methacry- late-co-quaternized dimethylaminoethyl methacrylate), poly(ethyl methacrylate-co-oleyl methac- rylate-co-diethylaminoethyl methacrylate), poly(diallyldimethylammonium chloride-co-acrylic acid), polyvinyl pyrrolidone-co-quaternized vinyl imidazole) and poly(acrylamide-co- Methacryloamidopropyl-pentamethyl-1 ,3-propylene-2-ol-ammonium dichloride), Suitable deposition aids include Polyquaternium-1 , Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-8, Polyquaternium-1 1 , Polyquaternium-14, Polyquaternium-22, Polyquaterni- um-28, Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33, as named under the International Nomenclature for Cosmetic Ingredients.
In one aspect, the deposition aid may comprise polyethyleneimine or a polyethyleneimine derivative. A suitable polyethyleneinine useful herein is that sold under the trade name Lupasol® by BASF, SE, and Ludwigshafen, Germany
In another aspect, the deposition aid may comprise a cationic acrylic based polymer. In a further aspect, the deposition aid may comprise a cationic polyacrylamide. In another aspect, the deposition aid may comprise a polymer comprising polyacrylamide and polymethacrylami- dopropyl trimethylammonium cation. In another aspect, the deposition aid may comprise poly (acrylamide- N-dimethyl aminoethyl acrylate) and its quaternized derivatives. In this aspect, the deposition aid may be that sold under the trade name Sedipur®, available from BTC Specialty Chemicals, a BASF Group, Florham Park, N.J. In a yet further aspect, the deposition aid may comprise poly (acrylamide-co-methacrylamidopropyltrimethyl ammonium chloride). In another aspect, the deposition aid may comprise a non-acrylamide based polymer, such as that sold under the trade name Rheovis® CDE, available from Ciba Specialty Chemicals, a BASF, SE group, Florham Park, N.J., or as disclosed in USPA 2006/0252668. In another aspect, the deposition aid may be selected from the group consisting of cationic or amphoteric polysaccharides. In one aspect, the deposition aid may be selected from the group consisting of cationic and amphoteric cellulose ethers, cationic or amphoteric galactomannan, cationic guar gum, cationic or amphoteric starch, and combinations thereof
Another group of suitable cationic polymers may include alkylamine-epichlorohydrin polymers which are reaction products of amines and oligoamines with epichlorohydrin, for example, those polymers listed in, for example, USPNs 6,642,200 and 6,551 ,986. Examples include dimethyl- amine-epichlorohydrin-ethylenediamine, available under the trade name Cartafix® CB and Cartafix® TSF from Clariant, Basle, Switzerland.
Another group of suitable synthetic cationic polymers may include polyamidoamine- epichlorohydrin (PAE) resins of polyalkylenepolyamine with polycarboxylic acid. The most common PAE resins are the condensation products of diethylenetriamine with adipic acid followed by a subsequent reaction with epichlorohydrin. They are available from Hercules Inc. of Wilmington DE under the trade name Kymene™ or from BASF SE (Ludwigshafen, Germany) under the trade name Luresin™ . The cationic polymers may contain charge neutralizing anions such that the overall polymer is neutral under ambient conditions. Non-limiting examples of suitable counter ions (in addition to anionic species generated during use) include chloride, bromide, sulfate, methylsulfate, sulfonate, methylsulfonate, carbonate, bicarbonate, formate, acetate, citrate, nitrate, and mixtures thereof.
The weight-average molecular weight of the polymer may be from about 500 Daltons to about 5,000,000 Daltons, or from about 1 ,000 Daltons to about 2,000,000 Daltons, or from about 2,500 Daltons to about 1 ,500,000 Daltons, as determined by size exclusion chromatography relative to polyethylene oxide standards with Rl detection. In one aspect, the MW of the cationic polymer may be from about 500 Daltons to about 37,500 Daltons.
Surfactants: The products of the present invention may comprise from about 0.1 1 % to 80% by weight of a surfactant. In one aspect, such compositions may comprise from about 5% to 50% by weight of surfactant. Surfactants utilized can be of the anionic, nonionic, zwitterionic, am- pholytic or cationic type or can comprise compatible mixtures of these types. Detergent surfactants useful herein are described in U.S. Patents 3,664,961 , 3,919,678, 4,222,905, 4,239,659, 6,136,769, 6,020,303, and 6,060,443.
Anionic and nonionic surfactants are typically employed if the fabric care product is a laundry detergent. On the other hand, cationic surfactants are typically employed if the fabric care product is a fabric softener.
Useful anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, or even from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the so- dium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyi group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (In- eluded in the term "alkyi" is the alkyi portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyi sulfates and alkyi alkoxy sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms).
Other useful anionic surfactants herein include the water-soluble salts of esters of o sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1 - sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and β-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyi group and from about 8 to 20 carbon atoms in the alkane moiety. In another embodiment, the anionic surfactant may comprise a C1 1 -C18 alkyi benzene sulfonate surfactant; a C10-C20 alkyi sulfate surfactant; a C10-C18 alkyi alkoxy sulfate surfactant, having an average degree of alkoxylation of from 1 to 30, wherein the alkoxy comprises a C1 - C4 chain and mixtures thereof; a mid-chain branched alkyi sulfate surfactant; a mid-chain branched alkyi alkoxy sulfate surfactant having an average degree of alkoxylation of from 1 to 30, wherein the alkoxy comprises a C1 -C4 chain and mixtures thereof; a C10-C18 alkyi alkoxy carboxylates comprising an average degree of alkoxylation of from 1 to 5; a C12-C20 methyl ester sulfonate surfactant, a C10-C18 alpha-olefin sulfonate surfactant, a C6-C20 sulfosuccin- ate surfactant, and a mixture thereof.
In addition to the anionic surfactant, the fabric care compositions of the present invention may further contain a nonionic surfactant. The compositions of the present invention can contain up to about 30%, alternatively from about 0.01 % to about 20%, more alternatively from about 0.1 % to about 10%, by weight of the composition, of a nonionic surfactant. In one embodiment, the nonionic surfactant may comprise an ethoxylated nonionic surfactant. Examples of suitable non-ionic surfactants are provided in U.S. Patents. 4,285,841 , 6,150,322, and
6,153,577.
. Suitable for use herein are the ethoxylated alcohols and ethoxylated alkyi phenols of the formula R(OC2H4)n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 20 carbon atoms and alkyi phenyl radicals in which the alkyi groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
Suitable nonionic surfactants are those of the formula R1 (OC2H4)nOH, wherein R1 is a C10 - C16 alkyi group or a C8 -C12 alkyi phenyl group, and n is from 3 to about 80. In one aspect, particularly useful materials are condensation products of C9-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol.
Additional suitable nonionic surfactants include polyhydroxy fatty acid amides such as N- methyl N-1 -deoxyglucityl cocoamide and N-methyl N-1 -deoxyglucityl oleamide and alkyi poly- saccharides such as the ones described in US 5,332,528. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647.
The fabric care compositions of the present invention may contain up to about 30%, alternatively from about 0.01 % to about 20%, more alternatively from about 0.1 % to about 20%, by weight of the composition, of a cationic surfactant. For the purposes of the present invention, cationic surfactants include those which can deliver fabric care benefits. Non-limiting examples of useful cationic surfactants include: fatty amines; quaternary ammonium surfactants; and imidazoline quat materials.
In some embodiments, useful cationic surfactants, include those disclosed in U.S. Patent Appli- cation number 2005/0164905 A1 and having the general formula (XIII):
Ri
R3 N— R, x
R2 (XIII)
wherein:
(a) R1 and R2 each are individually selected from the groups of: C1-C4 alkyl; C1-C4 hydroxy alkyl; benzyl; ~(CnH2nO)xH, wherein:
i. x has a value from about 2 to about 5;
ii. n has a value of about 1 -4;
(b) R3 and R4 are each:
i. a C8-C22 alkyl; or
ii. R3 is a C8-C22 alkyl and R4 is selected from the group of: C1 -C10 alkyl; C1 -C10 hydroxy alkyl; benzyl; ~(CnH2nO)xH, wherein:
1 . x has a value from 2 to 5; and
2. n has a value of 1 -4; and
(c) X is an anion. Fabric Softening Active Compounds- The fabric softening active may comprise, as the principal active, compounds of the following formula:
{R4-m - N+ - [X - Y - R1]m} X- (XIV) wherein each R may comprise either hydrogen, a short chain C1 -C6, in one aspect a C1 -C3 alkyl or hydroxyalkyl group, for example methyl, ethyl, propyl, hydroxyethyl, and the like, poly(C2-3 alkoxy), polyethoxy, benzyl, or mixtures thereof; each X may independently be (CH2)n, CH2-CH(CH3)- or CH-(CH3)-CH2-; each Y may comprise -0-(0)C-, -C(0)-0-, -NR- C(O)-, or -C(0)-NR-; each m may be 2 or 3; each n may be from 1 to about 4, in one aspect 2; the sum of carbons in each R1 , plus one when Y is -0-(0)C- or -NR-C(O) -, may be C12-C22, or C14-C20, with each R1 being a hydrocarbyl, or substituted hydrocarbyl group; and X- may comprise any softener-compatible anion. In one aspect, the softener-compatible anion may comprise chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate. In another aspect, the softener-compatible anion may comprise chloride or methyl sulfate.
In another aspect, the fabric softening active may comprise the general formula (XV): [R3N+CH2CH(YR1 )(CH2YR1 )] X- Formula (XV) wherein each Y, R, R1 , and X- have the same meanings as before. Such compounds include those having the formula (XVI):
[CH3]3 N(+)[CH2CH(CH20(0)CR1 )0(0)CR1 ] C1 (-)
(XVI) wherein each R may comprise a methyl or ethyl group. In one aspect, each R1 may comprise C15 to C19 group. As used herein, when the diester is specified, it can include the monoester that is present.
These types of agents and general methods of making them are disclosed in USPN 4,137,180. An example of a suitable DEQA (2) is the "propyl" ester quaternary ammonium fabric softener active comprising the formula 1 ,2-di(acyloxy)-3-trimethylammoniopropane chloride.
In one aspect, the fabric softening active may comprise the formula (XVII):
[R4-m - N+ - R1 m] X-
(XVII) wherein each R, R1 , m and X- have the same meanings as before.
In a further aspect, the fabric softening active may comprise the formula (XVIII):
Figure imgf000024_0001
(XVIII) wherein each R and Rl have the definitions given above; R2 may comprise a C1 -6 alkylene group, in one aspect an ethylene group; and G may comprise an oxygen atom or an -NR- group; and A- is as defined below.
In a yet further aspect, the fabric softening active may comprise the formula (XIX):
Figure imgf000025_0001
(XIX) wherein R1 , R2 and G are defined as above.
In a further aspect, the fabric softening active may comprise condensation reaction products of fatty acids with dialkylenetriamines in, e.g., a molecular ratio of about 2:1 , said reaction products containing compounds of the formula(XX):
R1— C(O)— N H— R2— N H— R3— N H— C(O)— R1
(XX) wherein R1 , R2 are defined as above, and R3 may comprise a C1 -6 alkylene group, or an ethylene group and wherein the reaction products may optionally be quaternized by the additional of an alkylating agent such as dimethyl sulfate. Such quaternized reaction products are described in additional detail in USPN 5,296,622.
In a yet further aspect, the fabric softening active may comprise the formula (XXI): [R1— C(O)— NR— R2— N(R)2— R3— NR— C(O)— R1 ]+ A- (XXI) wherein R, R1 , R2 and R3 are defined as above; A- is as defined below;
In a yet further aspect, the fabric softening active may comprise reaction products of fatty acid with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1 , said reaction products containing compounds of the formula (XXII):
R1 -C(0)-NH-R2-N(R30H)-C(0)-R1 (XXII) wherein R1 , R2 and R3 are defined as above;
In a yet further aspect, the fabric softening active may comprise the formula (XXIII):
Figure imgf000026_0001
(XXIII) wherein R, R1 and R2are defined as above; A- is as defined below.
In yet a further aspect, the fabric softening active may comprise the formula (XXIV);
Figure imgf000026_0002
Formula (XXIV) wherein;
X1 may comprise a C2-3 alkyl group, in one aspect, an ethyl group;
X2 and X3 may independently comprise C1 -6 linear or branched alkyl or alkenyl groups, in one aspect, methyl, ethyl or isopropyl groups;
R1 and R2 may independently comprise C8-22 linear or branched alkyl or alkenyl groups; characterized in that;
A and B are independently selected from the group comprising -0-(C=0)-, -(C=0)-0-, or mixtures thereof, in one aspect, -0-(C=0)-. Non-limiting examples of fabric softening actives comprising formula (XIV) are N, N-bis(stearoyl- oxy-ethyl) Ν,Ν-dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) Ν,Ν-dimethyl ammonium chloride, N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl ammonium methyl- sulfate. A non-limiting example of fabric softening actives comprising formula (XVI) is 1 , 2 di (stearoyl- oxy) 3 trimethyl ammoniumpropane chloride.
Non-limiting examples of fabric softening actives comprising formula (XVII) may include dial- kylenedimethylammonium salts such as dicanoladimethylammonium chloride,
di(hard)tallowdimethylammonium chloride dicanoladimethylammonium methylsulfate,. An ex- ample of commercially available dialkylenedimethylammonium salts usable in the present invention is dioleyldimethylammonium chloride available from Witco Corporation under the trade name Adogen® 472 and dihardtallow dimethylammonium chloride available from Akzo Nobel Arquad 2HT75.
A non-limiting example of fabric softening actives comprising formula (XVIII) may include 1 - methyl-1 -stearoylamidoethyl-2-stearoylimidazolinium methylsulfate wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group, R5 is a methyl group and A- is a methyl sulfate anion, available commercially from the Witco Corporation under the trade name Varisoft®.
A non-limiting example of fabric softening actives comprising formula (XIX) is 1 - tallowylamidoethyl-2-tallowylimidazoline wherein R1 may comprise an acyclic aliphatic C15-C17 hydrocarbon group, R2 may comprise an ethylene group, and G may comprise a NH group.
A non-limiting example of a fabric softening active comprising formula (XX) is the reaction products of fatty acids with diethylenetriamine in a molecular ratio of about 2:1 , said reaction product mixture comprising N,N"-dialkyldiethylenetriamine having the formula (XXV): R1 -C(0)-NH-CH2CH2-NH-CH2CH2-NH-C(0)-R1
Formula (XXV) wherein R1 is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021 , available from Henkel Corporation, and R2 and R3 are divalent ethylene groups. A non-limiting example of Compound (XXI) is a difatty amidoamine based softener having the formula (XXVI):
[R1 -C(0)-NH-CH2CH2-N(CH3)(CH2CH20H)-CH2CH2-NH-C(0)-R1 ]+ CH3S04-
Formula (XXVI) wherein R1 is an alkyl group. An example of such compound is that commercially available from the Witco Corporation e.g. under the trade name Varisoft® 222LT.
An example of a fabric softening active comprising formula (XXII) is the reaction products of fatty acids with N-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1 , said reaction product mixture comprising the formula (XXVII):
R1 -C(0)-NH-CH2CH2-N(CH2CH20H)-C(0)-R1
Formula (XXVII) wherein R1 -C(0) is an alkyl group of a commercially available fatty acid derived from a vegetable or animal source, such as Emersol® 223LL or Emersol® 7021 , available from Henkel Cor- poration.
An example of a fabric softening active comprising formula (XXIII) is the diquaternary compound having the formula (XXVIII):
Figure imgf000028_0001
Formula (XXVIII) wherein R1 is derived from fatty acid. Such compound is available from Witco Company.
A non-limiting example of a fabric softening active comprising formula (XXIV) is a dialkyl imidazoline diester compound, where the compound is the reaction product of N-(2-hydroxyethyl)- 1 ,2-ethylenediamine or N-(2-hydroxyisopropyl)-1 ,2-ethylenediamine with glycolic acid, esterified with fatty acid, where the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydro- genated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid or a mixture of the above.
It will be understood that combinations of softener actives disclosed above are suitable for use herein.
Anion A In the cationic nitrogenous salts herein, the anion A-, which comprises any softener compatible anion, provides electrical neutrality. Most often, the anion used to provide electrical neutrality in these salts is from a strong acid, especially a halide, such as chloride, bromide, or iodide. However, other anions can be used, such as methylsulfate, ethylsulfate, acetate, formate, sulfate, carbonate, and the like. In one aspect, the anion A may comprise chloride or methylsulfate. The anion, in some aspects, may carry a double charge. In this aspect, A- represents half a group.
In one aspect, the fabric care and/or treatment composition may comprise a second softening agent selected from the group consisting of polyglycerol esters (PGEs), oily sugar derivatives, and wax emulsions. Suitable PGEs include those disclosed in USPA 61/089,080. Suitable oily sugar derivatives and wax emulsions include those disclosed in USPA 2008-0234165 A1.
In one aspect, the compositions may comprise from about 0.001 % to about 0.01 % of an unsaturated aldehyde. In one aspect, the compositions are essentially free of an unsaturated aldehyde. Without being limited by theory, in this aspect, the compositions are less prone to the yellowing effect often encountered with amino-containing agents.
Builders - The compositions may also contain from about 0.1 % to 80% by weight of a builder. Compositions in liquid form generally contain from about 1 % to 10% by weight of the builder component. Compositions in granular form generally contain from about 1 % to 50% by weight of the builder component. Detergent builders are well known in the art and can contain, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders. Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhy- droxy sulfonates. Examples of polyacetate and polycarboxylate builders are the sodium, potas- sium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S. 4,144,226 and U.S. 4,246,495. Other polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuc- cinate and tartrate disuccinate described in U.S. 4,663,071 , Builders for use in liquid detergents are described in U.S. 4,284,532, One suitable builder includes may be citric acid. Suitable nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates, such as sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of Si02 to alkali metal oxide of from about 0.5 to about 4.0, or from about 1.0 to about 2.4. Also useful are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in U.S. 4,605,509. Dispersants - The compositions may contain from about 0.1 %, to about 10%, by weight of dis- persants Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may contain at least two carboxyl radicals separated from each other by not more than two carbon atoms. The dispersants may also be alkoxylated derivatives of polyamines, and/or quaternized derivatives thereof such as those described in US 4,597,898, 4,676,921 , 4,891 ,160, 4,659,802 and 4,661 ,288.
Enzymes - The compositions may contain one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include hemi- cellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, lig- ninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination may be a cocktail of conventional applicable enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase. Enzymes can be used at their art-taught levels, for example at levels recommended by suppliers such as Novozymes and Genencor. Typical levels in the compositions are from about 0.0001 % to about 5%. When enzymes are present, they can be used at very low levels, e.g., from about 0.001 % or lower; or they can be used in heavier- duty laundry detergent formulations at higher levels, e.g., about 0.1 % and higher. In accord- ance with a preference of some consumers for "non-biological" detergents, the compositions may be either or both enzyme-containing and enzyme-free.
Dye Transfer Inhibiting Agents - The compositions may also include from about 0.0001 %, from about 0.01 %, from about 0.05% by weight of the compositions to about 10%, about 2%, or even about 1 % by weight of the compositions of one or more dye transfer inhibiting agents such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
Chelant - The compositions may contain less than about 5%, or from about 0.01 % to about 3% of a chelant such as citrates; nitrogen-containing, P-free aminocarboxylates such as EDDS, EDTA and DTPA; aminophosphonates such as diethylenetriamine pentamethylenephosphonic acid and, ethylenediamine tetramethylenephosphonic acid; nitrogen-free phosphonates e.g., HEDP; and nitrogen or oxygen containing, P-free carboxylate-free chelants such as compounds of the general class of certain macrocyclic N-ligands such as those known for use in bleach catalyst systems.
Brighteners - The compositions may also comprise a brightener (also referred to as "optical brightener") and may include any compound that exhibits fluorescence, including compounds that absorb UV light and reemit as "blue" visible light. Non-limiting examples of useful brighteners include: derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, five-membered heterocy- cles such as triazoles, pyrazolines, oxazoles, imidiazoles, etc., or six-membered heterocycles (coumarins, naphthalamide, s-triazine, etc.). Cationic, anionic, nonionic, amphoteric and zwit- terionic brighteners can be used. Suitable brighteners include those commercially marketed under the trade name Tinopal-UNPA-GX® by Ciba Specialty Chemicals Corporation, a BASF, SE group; (High Point, NC).
Bleach system - Bleach systems suitable for use herein contain one or more bleaching agents. Non-limiting examples of suitable bleaching agents include catalytic metal complexes; activated peroxygen sources; bleach activators; bleach boosters; photobleaches; bleaching enzymes; free radical initiators; H202; hypohalite bleaches; peroxygen sources, including perborate and/or percarbonate and combinations thereof. Suitable bleach activators include perhydrolyz- able esters and perhydrolyzable imides such as, tetraacetyl ethylene diamine, octanoylcaprolac- tam, benzoyloxybenzenesulphonate, nonanoyloxybenzene-'sulphonate, benzoylvalerolactam, dodecanoyloxybenzenesulphonate. Suitable bleach boosters include those described in US Patent 5,817,614. Other bleaching agents include metal complexes of transitional metals with ligands of defined stability constants. Such catalysts are disclosed in U.S. 4,430,243,
5,576,282, 5,597,936 and 5,595,967.
Stabilizer - The compositions may contain one or more stabilizers and thickeners. Any suitable level of stabilizer may be of use; exemplary levels include from about 0.01 % to about 20%, from about 0.1 % to about 10%, or from about 0.1 % to about 3% by weight of the composition. Non- limiting examples of stabilizers suitable for use herein include crystalline, hydroxyl-containing stabilizing agents, trihydroxystearin, hydrogenated oil, or a variation thereof, and combinations thereof. In some aspects, the crystalline, hydroxyl-containing stabilizing agents may be water- insoluble wax-like substances, including fatty acid, fatty ester or fatty soap. In other aspects, the crystalline, hydroxyl-containing stabilizing agents may be derivatives of castor oil, such as hydrogenated castor oil derivatives, for example, castor wax. The hydroxyl containing stabilizers are disclosed in US Patents 6,855,680 and 7,294,61 1 . Other stabilizers include thickening stabilizers such as gums and other similar polysaccharides, for example gellan gum, carrageenan gum, and other known types of thickeners and rheological additives. Exemplary stabilizers in this class include gum-type polymers (e.g. xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof including cellulose ethers and cellulose esters and tamarind gum (for example, comprising xyloglucan polymers), guar gum, locust bean gum (in some aspects comprising galactomannan polymers), and other industrial gums and polymers. For the purposes of the present invention, the non-limiting list of adjuncts illustrated hereinafter are suitable for use in the instant compositions and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. It is understood that such adjuncts are in addition to the components that are supplied via Applicants' perfumes and/or perfume systems. The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable adjunct materials include, but are not limited to, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and/or pigments. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incor- porated by reference.
Silicones - Suitable silicones comprise Si-0 moieties and may be selected from (a) non- functionalized siloxane polymers, (b) functionalized siloxane polymers, and combinations thereof. The molecular weight of the organosilicone is usually indicated by the reference to the viscosity of the material. In one aspect, the organosilicones may comprise a viscosity of from about 10 to about 2,000,000 centistokes at 25oC. In another aspect, suitable organosilicones may have a viscosity of from about 10 to about 800,000 centistokes at 25oC. Suitable organo- silicones may be linear, branched or cross-linked. In one aspect, the organosilicones may be linear.
The present invention will be disclosed further by the following non-limiting examples:
The present invention will be disclosed further by the following non-limiting examples:
Examples:
Examples of Polyisobutene Premixes (PM):
Assessment of the Premixes and Formulations:
The premixes or formulations are assessed "clear", when the transmittance of the formulation, measured with a CADAS 200 spectrophotometer (Dr. Lange Company) at 650 nm in a 1 cm cuvette is higher than 90%. The premix or formulations are assessed "homogeneous", when upon visual inspection no creaming / sedimentation or phase separation can be observed after one day. The premixes or formulations are assessed "phase separated" when the mixture separated into clearly recognizable organic and aqueous phases, or if droplets of organic phase could be observed on top of the aqueous phase. Example: Polyisobutene Premix PM1
Polyisobutene (6.0 g, 60 parts per weight, molecular weight 1000 g/mol) and polyisobutene succinic anhydride (3.0 g, 30 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The mixture was heated to 80°C to reduce viscosity and thus simplify mixing. Nonionic surfactant C10-Guerbetalcohol alkoxylate (HLB 12.5) (1.0 g, 10 parts per weight) was added and the resulting mixture was stirred for 5 min, yielding an emulsifiable polyisobutene composition PM1 in the form of a homogeneous, clear and stable solution.
Example: Polyisobutene Premixes PM2 - PM5
The mixture is prepared in the same way as Example PM1 , applying the ratios given in the table below. All examples formed homogeneous, clear and stable solutions.
Example PIB PIBSA Surfactant Solution properties
[wt.-%] [wt.-%] [wt.-%]
PM1 60 30 10 Homogeneous, clear, stable
PM2 70 20 10 Homogeneous, clear, stable
PM3 40 35 25 Homogeneous, clear, stable
PM4 40 45 15 Homogeneous, clear, stable
PM5 40 55 5 Homogeneous, clear, stable
Example: Polyisobutene Premix PM6
Polyisobutene (6.0 g, 60 parts per weight, molecular weight 1000 g/mol) and polyisobutene succinic anhydride (3.0 g, 30 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The mixture was heated to 80°C to reduce viscosity and thus simplify mixing. A surfactant mixture of nonionic surfactants C13-oxoalcohol + 3 EO (HLB 9) (0.5 g, 5 parts per weight) and C13-oxoalcohol + 8 EO (HLB 13) (0.5 g, 5 parts per weight) was added and the resulting mixture was stirred for 5 min, yielding an emulsifiable polyisobutene composition PM6 in the form of a homogeneous, clear and stable solution. Example: Polyisobutene Premixes PM7 - PM10:
The following examples were done analogous to example PM3, taking the composition given in the table.
Example PIB PIBSA Surfactant Mix Solution properties
[wt.-%] [wt.-%] [wt.-%]
PM6 60 30 10 Homogeneous, clear, stable
PM7 70 20 10 Homogeneous, clear, stable
PM8 40 35 25 Homogeneous, clear, stable
PM9 40 45 15 Homogeneous, clear, stable
PM10 40 55 5 Homogeneous, clear, stable
The following comparative examples were done analogous to example PM3, taking the composition given in the table below. All emulsions resulted in an unstable premix solution that showed turbidity or phase separation when the amount of surfactant was equal to or higher than the amount of polymeric emulsifier (PIBSA): Comparative Example PIB PIBSA Surfactant Mix Solution properties
[wt.-%] [wt.-%] [wt.-%]
Comp.Ex.4 70 5 25 Phase Separation
Comp.Ex.5 80 5 15 Phase Separation
Comp.Ex.6 90 5 5 Phase Separation
Example: Polyisobutene Premix PM1 1
Polyisobutene (5.0 g, 50 parts per weight, molecular weight 1000 g/mol) , polyisobuteneamine (3.25 g, 32.5 parts per weight) and n-paraffin C5-C20 (1 .75 g, 17.5 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The composition is a homogeneous, clear and stable solution. Example: Polyisobutene Premix PM12
Polyisobutene (4.0 g, 40 parts per weight, molecular weight 1000 g/mol) , polyisobuteneamine (3.9 g, 39.0 parts per weight) and n-paraffin C5-C20 (2.1 g, 21.0 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The composition is a homogeneous, clear and stable solution.
Example: Polyisobutene Premix PM13
Polyisobutene (1 .0 g, 10 parts per weight, molecular weight 1000 g/mol) , polyisobuteneamine (5.85 g, 58.5 parts per weight) and n-paraffin C5-C20 (3.15 g, 31.5 parts per weight) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The composition is a homogeneous, clear and stable solution.
Example: Polyisobutene Premix PM14
Polyisobutene (24.0 g, molecular weight 1000 g/mol) and polyisobutene succinic anhydride ( 12.0 g) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The mixture is heated to 80°C to reduce viscosity and thus simplify mixing. A mixture of nonionic surfactant C10-Guerbetalcohol alkoxylate (HLB 12.5) (4.0 g) and water (2.0 g) is added and the mixture is stirred for 30 min, yielding an emulsifiable polyisobutene composition in the form of a homogeneous clear stable solution. Example: Polyisobutene Premix PM15
Polyisobutene (24.0 g, molecular weight 1000 g/mol) and polyisobutene succinic anhydride (12.0 g) were mixed in a 25ml glass vial and stirred at low shear with a magnetic stirrer bar. The mixture is heated to 80°C to reduce viscosity and thus simplify mixing. Nonionic surfactant C10- Guerbetalcohol alkoxylate (HLB 12.5) (4.0 g) is added and the mixture is stirred for 5min. Sub- sequently, water (2 g) is added and the mixture is stirred for another 5 min, yielding an emulsifi- yable polyisobutene composition in the form of a homogeneous clear stable solution. Examples of Formulations (F) of Polyisobutylene Premixes in Liquid Detergents
The cleaning and/or treatment compositions of the present invention can be formulated into any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. 5,879,584; U.S. 5,691 ,297; U.S. 5,574,005; U.S. 5,569,645; U.S. 5,565,422; U.S. 5,516,448; U.S. 5,489,392; U.S. 5,486,303 all of which are incorporated herein by reference.
Preparation of a Standard Liquid Detergent Formulation (A):
Liquid detergent fabric care compositions of Example A were made by mixing together the ingredients listed in the proportions shown;
Figure imgf000035_0001
1 Available from Shell Chemicals, Houston, TX.
2 Available from Sasol Chemicals, Johannesburg, South Africa
4 Available from Evonik Corporation, Hopewell, VA.
5 Available from The Procter & Gamble Company, Cincinnati, OH.
6 Available from Sigma Aldrich chemicals, Milwaukee, Wl
7 Available from Genencor International, South San Francisco, CA.
8 Available from Ciba Specialty Chemicals, High Point, NC
9 600 g/mol molecular weight polyethylenimine core with 20 ethoxylate groups per -NH and available from BASF (Ludwigshafen, Germany) Example F1 :
Liquid detergent formulation A (97.80 g) was placed in a 150 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene Premix PM1 (2.20 g) was slowly added to the detergent formulation upon stirring. The resulting turbid polyisobutene containing formula- tion was stirred for another 30 min to form a homogeneous, clear and stable formulation.
Examples F2 -F8:
The following examples, summarized in Table 1 were prepared in the same way as described in Example F1 , applying the polyisobutene premixes and amounts given in the table. The charac- teristics of the formulation are also described in table 1.
Elxampi
Table 1
Plitt Dueneoyso
Piremx hi O J2
f Atmoun o
Fli Atormuaon
F1 PM1 97.8 2 Atmoun.2 Clear, homogeneous
F2 PM2 97.8 2.2 Piremx Clear, homogeneous
F3 PM3 97.7 2.3 Clear, homogeneous
F4 PM4 97.8 2.2 Clear, homogeneous
f Atspec o
F5 PM5 97.9 2.1 Clear, homogeneous
Flitormuaon
F6 PM6 97.8 2.2 Clear, homogeneous
F7 PM7 97.8 2.2 Clear, homogeneous
F8 PM8 97.7 2.3 Clear, homogeneous
F9 PM9 97.8 2.2 Clear, homogeneous
F10 PM10 97.9 2.1 Clear, homogeneous
F12 PM1 1 98.0 2.0 Slightly turbid, Transr
F13 PM12 98.0 2.0 Clear, homogeneous
F14 PM13 98.0 2.0 Clear, homogeneous
Comparative Example CF1 :
Liquid detergent formulation A (98.0 g) was placed in a 150 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (2.0 g, molecular weight = 1000 g/mol) was slowly added to the detergent formulation upon stirring. The resulting turbid polyisobutene containing formulation was stirred for another 30 min to form a phase-separated turbid mixture with a ring of polyisobutene on top of the liquid level.
Examples of Formulations (F) of Polyisobutylene Premixes in Liquid Fabric Enhancers:
Preparation of a Standard Liquid Fabric Enhancer Formulation (B):
Rinse-Added fabric care compositions were prepared by mixing together ingredients shown below: Ingredient B
Fabric Softener Active1 1 1.0
Lutensol XL-702 1 .0
Quaternized polyacrylamide4 0.25
Calcium chloride3 0.15
Ammonium chloride3 0.1
Alkyl siloxane polymer6 1 .5
Perfume 1 .75
Perfume microcapsule5 0.69
Water, suds suppressor, stabilizers, pH control agents, buffers, to 100% pH = 3.0 dyes & other optional ingredients
1 N,N-di(tallowoyloxyethyl) - N,N dimethylammonium chloride available from Evonik Corporation, Hopewell, VA.
2 Available from BASF (Ludwigshafen, Germany)
3 Available from Sigma Aldrich chemicals, Milwaukee, Wl
4 Cationic polyacrylamide polymer such as a copolymer of acrylamide/[2- (acryloylamino)ethyl]tri-methylammonium chloride (quaternized dimethyl aminoethyl acry- late) available from BASF, AG, Ludwigshafen under the trade name Sedipur® 544.
5 Available from Appleton Paper of Appleton, Wl
6 Aminofunctional silicone available from Shin-Etsu Silicones, Akron, OH
Example F15:
Fabric softener formulation B (98.0 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM1 1 (2.0 g) was slowly added to the fabric softener formulation upon stirring. The resulting polyisobutene containing fabric softener formulation was stirred for another 30 min to form a homogeneous stable formulation that did not show any signs of phase separation. Example F16:
The example is prepared analogous to Example F15, with the difference that the Polyisobutene premix PM1 1 is colored with a red, oil-soluble and water-insoluble dye (Sudan Red 7B, Sigma- Aldrich, 20 ppm) and the liquid fabric enhancer is colored with a blue, water-soluble and oil- insoluble dye (Liquitint Blue, Milliken, 20 ppm). The resulting polyisobutene containing formula- tion exhibited a homogeneous, violet color as a result of the perfect emulsification of the water phase and the oil phase, showing not sign of creaming / sedimentation (i.e. no clear blue aqueous phase on top or bottom), as well as not sign of phase separation (i.e. no red oil phase or red oil droplets observable). Example F17:
Fabric softener formulation B (98.0 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (2.0 g) was slowly added upon stirring. The resulting polyisobutene containing fabric softener formulation was stirred for another 30 min to form a homogeneous stable formulation that did not show any signs of phase separation.
Example F18:
The example was prepared analogous to Example F17, with the difference that the Polyisobu- tene premix PM5 is colored with a red, oil-soluble and water-insoluble dye (Sudan Red 7B,
Sigma-Aldrich, 20 ppm) and the liquid fabric enhancer is colored with a blue, water-soluble and oil-insoluble dye (Liquitint Blue, Milliken, 20 ppm). The resulting polyisobutene containing formulation exhibited a homogeneous, violet color as a result of the perfect emulsification of the water phase and the oil phase, showing not sign of creaming / sedimentation (i.e. no clear blue aque- ous phase on top or bottom), as well as not sign of phase separation (i.e. no red oil phase or red oil droplets observable).
Comparative Example CF2:
Fabric softener formulation B (98.0 g) that is colored with a blue, water-soluble and oil-insoluble dye (Liquitint Blue, Milliken, 20 ppm) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (2.0 g, 1000 g/mol), colored with a red, oil-soluble and water-insoluble dye (Sudan Red 7B, Sigma-Aldrich, 20 ppm) was slowly added to the fabric softener formulation upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a clearly phase-separated product consisting of a polyisobutene phase forming a red-colored ring at the top of the liquid level and a liquid fabric enhancer phase forming a blue aqueous phase.
Examples of Formulations (F) of Polyisobutylene Premixes in Hand Dishwash Formulations: Standard Liquid Hand Dishwash Formulation:
The following are non-limiting examples of Liquid Hand Dish Wash formulation compositions prepared by mixing together ingredients shown below.
Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9
Lial AE0.6S 25.4 25.4 25.4
AE3S 12.0 28.7
Lial 31.7 39.6 44.4 52.3
AExS 13.0 13.0 13.0 16.3 20.4 22.8 26.9
AO 3.2 3.2 3.2 4.0 3.3 3.8 4.7 5.3 6.3
TMBA 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06
HEDP 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Ethanol 3.0 3.0 3.0 3.0 3.0 2.5 2.5 2.5 2.5
NaCI 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0 1 .0
Polypropyleneglycol 0.4 0.5 0.5 0.5 0.5
Sodium citrate 5
Water, suds suppressor, stabilizers, pH control agents,
buffers, dyes & other optional ingredients
To 100%
Lial AE0.6S - anionic alkyl(ether)0.6sulphate surfactant and amine oxide
AE3S - anionic alkyl(ether)3sulphate surfactant and amine oxide
Lial - commercially available light duty liquid paste from Sasol containing anionic AES surfactant and amphoteric amine oxide
AExS - C10-C18 alkyl alkoxy sulphate surfactants wherein preferably x is from 1 -30
AO - total quantity of amine oxides in final product
TMBA is trimethoxy benzoic acid
HEDP is 1 -hydroxyethylidene 1 ,1 -diphosphonic acid
Example F19:
The hand dishwash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM1 (1 .1 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a slightly turbid, homogeneous liquid. Example F20:
The hand dishwash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM2 (1 .1 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a turbid, homogeneous liquid.
Example F21 :
The hand dishwash formulation (50g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (1.54 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a clear homogeneous liquid.
Comparative Example CF3:
The hand dishwash formulation (50g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (molecular weight 1000 g/mol, 1.0 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a turbid liquid with clearly phase separated droplets of polyisobutene on top of the liquid.
Examples of Formulations (F) of Polyisobutylene Premixes in Cosmetic Formulations: Standard Shampoo and Bodywash Formulation:
Cocoamidopropylbetaine (12.5 g, 29.5 % active in water) and sodium laureth sulfate (35.7 g, 29 % active) were mixed with demineralized water (51.8 g) to form a standard shampoo or body- wash formulation. The product can be thickened with 1 .0 g of sodium chloride.
Example F22
The standard shampoo and bodywash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM1 (1 .1 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a turbid, homogeneous liquid.
Example F23
The standard shampoo and bodywash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM2 (1 .1 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a turbid, homogeneous liquid. Example F24
The standard shampoo and bodywash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (1.54 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a slightly turbid liquid that shows slight creaming upon storage.
Comparative Example CF4:
The standard body wash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (molecular weight 1000, 1.0 g) was slowly added upon stirring. The resulting polyisobutene mixture was stirred for another 30 min to form a turbid inhomogeneous liquid that instantaneously shows creaming. Examples of Formulations (F) of Polyisobutylene Premixes in Car Wash Formulations:
Standard Car Wash Shampoo for Home Use:
Dodecylbenzenesulfonate amine salt (20 g, 55% active in water), C10-Guerbetalcohol+7EO (HLB 12.5) (2 g, 100% active) and alkylpolyglucoside (2 g, 70% active) were mixed with water (76 g) to form a standard car shampoo formulation for home users.
Example F25:
The standard car wash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM1 (1 .1 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form a slightly turbid, homogeneous liquid.
Example F26:
The standard car wash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (1 .54 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form an opaque homogenous liquid.
Comparative Example CF5:
The standard car wash formulation (50 g) was placed in a 100 ml glass beaker and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (molecular weight 1000 g/mol, 1 .54 g) was slowly added upon stirring. The resulting polyisobutene containing formulation was stirred for another 30 min to form an inhomogenous, turbid liquid that instantaneously showed creaming and phase separation.
Conductivity measurememts:
Conductivity is measured at room temperature with a conductometer "LF 320" of "Wis- sentschaftlich-Technische Werkstatten GmbH". The measurement probe is a TetraCon 325 with a cell constant of 0.466 cm-1. Sample Conductivity ^S/cm]
Distilled Water (Lab) 8.0
C10-Guerbetalcohol alkoxylate (HLB 12.5) 0.4
C13-oxoalcohol + 3 EO (HLB 9) 0.4
C13-oxoalcohol + 8 EO (HLB 13) 0.4
Polyisobutene amine (PIBA) 0.1
Polyisobutene (PIB, MW 1000) 0.2
Polyisobutene Succinic Anhydride (PIBSA) 0.2
Premix PM1 0.2
Premix PM2 0.2
Premix PM5 0.2
Premix PM5 + 5% Water 0.2
Premix PM5 + 10% Water 0.2 As can be seen from the measurements, all premixes display the same conductivity as the hydrophobic components such as PIB or PIBA, showing that water is not the continuous phase in these premixes.

Claims

Claims:
Self-emulsifiable composition containing
a) polyolefine(s) in an amount of from 5 to 90 weight %,
b) polymeric emulsifier(s) Px in an amount of from 5 to 90 weight %,
c) oil(s) Ox in an amount of from 0 to 40 weight %,
d) surfactant(s) Sx in an amount of from 0 to 40 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range of from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25.
Self-emulsifiable composition according to claim 1 , wherein the components independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 20 to 70 weight %,
b) polymer emulsifier(s) Px in an amount of from 10 to 50 weight %,
c) oil(s) Ox in an amount of from 0 to 40 weight %,
d) surfactant(s) Sx in an amount of from 0.1 to 30 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range of from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25.
Self-emulsifiable composition according to claim 1 or 2, wherein the components independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 30 to 60 weight %,
b) polymer emulsifier(s) Px in an amount of from 20 to 45 weight %,
c) oil(s) Ox in an amount of from 0,1 to 30 weight %,
d) surfactant(s) Sx in an amount of from 0,5 to 25 weight %,
e) additive(s) Ax in an amount of from 0,1 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher thanl .25. Self-emulsifiable composition according to claim 1 to 3, wherein the components independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 40 to 50 weight %,
b) polymeric emulsifier(s) Px in an amount of from 25 to 40 weight %,
c) oil(s) Ox in an amount of from 5 to 15 weight %,
d) surfactant(s) Sx in an amount of from 5 to 15 weight %,
e) additive(s) Ax in an amount of from 2 to 8 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from 4:1 to 1 :3 and the weight ratio of Px to Sx is higher than 1.25.
Self-emulsifiable composition according to claim 1 to 4, wherein the composition is a water-free composition.
Self-emulsifiable composition according to claim 1 to 4, wherein the composition is a water-reduced composition.
Self-emulsifiable composition according to claim 1 to 6, wherein the polyolefine(s) is/are selected from the group consisting of: polyethylene, polypropylene, polybutylene and poly- isobutene.
Self-emulsifiable composition according to claim 1 to 7, wherein the polymeric emulsifi- er(s) Px is/are selected from the group consisting of
P1 ) polyisobutene derivatives, wherein P1 is polyisobutenamine, polyisobutene succinic anhydride, a copolymer of polyisobuten succinic anhydride with polyalkylene glycol, a copolymer of polyisobuten succinic anhydride with an oligoamine or with an oligoamine alkoxylate,
P2) polymeric cationic emulsifiers, wherein P2 is the result of the polymerization of
A2) one or more cationic ethylenically unsaturated monomers
B2) one or more linear or branched alkyl(meth)acrylates,
C2) from 0 to 30 weight % of one or more C3-C8 monoethylenically unsaturated car- boxylic acids, P3) being copolymers of polyalkylene(s) of formula 3
Figure imgf000046_0001
3
wherein:
R* = H, CH3,
R = H, methyl,
R' = H, methyl,
n = 1 to 200,
with monoethylenically unsaturated monomers.
9. Self-emulsifiable composition according to claim 1 to 8, wherein the polymer(s) Px is/are se lected from the group consisting of
P1 ) polyisobutene derivatives, wherein P1 is polyisobutenamine, polyisobutene succinic an- hydride, a copolymer of polyisobuten succinic anhydride and polyethylene glycol,
P2) polymeric cationic emulsifiers, wherein P2 is the result of the polymerization of
A2) diallyl dimethyl ammonium chloride,
B2) one or more linear or branched alkyl(meth)acrylates,
C2) from 0 to 30 weight % of acrylic acid.
P3) being copolymers of polyalkylene(s) of formula 3
Figure imgf000046_0002
3
wherein:
R* = H, CH3,
R = H, methyl, = H, methyl,
1 to 200,
with monoethylenically unsaturated monomers
Self-emulsifiable composition according to claim 1 to 9, wherein the oil(s) Ox is/are selected from the group consisting of:
c1 ) mineral oils, having a boiling point at atmospheric pressure of 150 °C or higher c2) esters of Cio- to C26-carboxylic acid with C& - C24-alcohols and
c3) silicone oils.
Self-emulsifiable composition according to claim 1 to 10, wherein the surfactant(s) Sx is/are selected from the group consisting of:
d1 ) nonionic surfactants,
d2) anionic surfactants and
d3) cationic surfactants.
Self-emulsifiable composition according to claim 1 to 1 1 , which has a content of organic solvent below 50 mg/kg of composition.
Use of an emulsion according to claims 1 to 12 in chemical technical applications, cosmetics, plant protection, preparation and treatment of paper, textiles and leather, adhe- sives, dye and pigment formulations, coatings, pharmaceutical applications, construction, wood treatment.
14. Use of an emulsion according to claims 1 to 12 in car wash, laundry detergent compositions, hard surface cleaners, automatic dishwashing liquids and dishwashing liquids
PCT/EP2012/072162 2011-11-11 2012-11-08 Self-emulsifiable polyolefine compositions WO2013068479A1 (en)

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